Process for producing particles of amine reaction product

ABSTRACT

There is provided a process for producing particles of amine reaction product by means of a carrier having a melting point between 30 degrees Celsius and 135 degrees Celsius, optionally followed by a coating step. Processed amine reaction products and finished compositions incorporating such processed product are also herein provided.

FIELD OF THE INVENTION

The present invention relates to a process for producing particles ofamine reaction product.

BACKGROUND OF THE INVENTION

Perfumed products are well-known in the art. However, consumeracceptance of such perfumed products like laundry and cleaning productsis determined not only by the performance achieved with these productsbut also by the aesthetics associated therewith. The perfume componentsare therefore an important aspect of the successful formulation of suchcommercial products.

It is also desired by consumers for treated fabrics to maintain thepleasing fragrance over time. Indeed, perfume additives make suchcompositions more aesthetically pleasing to the consumer, and in somecases the perfume imparts a pleasant fragrance to fabrics treatedtherewith. However, the amount of perfume carried-over from an aqueouslaundry bath onto fabrics is often marginal and does not last long onthe fabric. Furthermore, fragrance materials are often very costly andtheir inefficient use in laundry and cleaning compositions andineffective delivery to fabrics results in a very high cost to bothconsumers and laundry and cleaning manufacturers. Industry, therefore,continues to seek with urgency for more efficient and effectivefragrance delivery in laundry and cleaning products, especially forimprovement in the provision of long-lasting fragrance to the fabrics.

It has recently been found that an amine reaction product of a compoundcontaining a primary amine functional group and an active ketone oraldehyde containing component fulfills such a need. Disclosure of suchcompounds can be found in recently filed applications EP 98870227.0, EP98870226.2, EP 99870026.4, and EP 99870025.6, all incorporated herein byreference.

However, a problem now encountered with the use of these compound istheir ease of incorporation into fully formulated compositions. Indeed,such amine reaction products are often viscous which renders theirincorporation into these fully formulated compositions more cumbersome.

It is therefore an object of the invention to provide amine reactionproduct in a form suitable for easy incorporation into fully formulatedcomposition.

It has now been found that the mixing of the amine reaction product witha carrier having specific melting point to form a particle fulfills sucha need. Preferably, the obtained particle is thereafter treated to forma coated particle.

Further, it has also been advantageously found that both viscous andnon-viscous amine reaction product when processed by the presentinvention exhibit better deposition and long lasting release than aminereaction product which have not been processed according to thisprocess. Not to be bound by theory, it is believed that the mixing withsuch carrier act as a shell around the amine reaction product, thusprotecting it from the aggressive wash liquor as well as enhancing itsfabric deposition properties.

By “viscous”, it is meant a product which has a viscosity higher than1000 cps. The viscosity is measured on a rheometer, TA Instrument CSL²₁₀₀ at a temperature of 25 C. with a gap setting of 500 microns.

The carrier for use herein has a melting point, measured at atmosphericpressure, of from 30° C. to 135° C.

SUMMARY OF THE INVENTION

The present invention is a process for making particles of aminereaction product of a compound containing a primary and/or secondaryamine functional group and an active ketone or aldehyde containingcomponent, and which comprises the steps of:

a)-providing the amine reaction product, and

b)-mixing therewith a carrier having a melting point of from 30° C. to135° C.

In a preferred embodiment of the invention, the obtained particle isfurther processed to form a coated particle.

DETAILED DESCRIPTION OF THE INVENTION

Starting Materials

1)-Amine Reaction Product

The amine reaction product for use herein is a product of reactionbetween a compound containing a primary and/or secondary aminefunctional group and an active ketone or aldehyde containing component,so called hereinafter “amine reaction product”.

A typical disclosure of amine reaction product suitable for use hereincan be found in recently filed applications EP 98870227.0, EP98870226.2, EP 99870026.4, and EP 99870025.6, all incorporated herein byreference.

A-Primary and/or secondary amine

By “primary and/or secondary amine”, it is meant a component whichcarries at least one primary and/or secondary amine and/or amidefunction.

Preferably, the primary and/or secondary amine compound is alsocharacterized by an Odour Intensity Index of less than that of a 1%solution of methylanthranilate in dipropylene glycol.

Odour Intensity Index Method

By Odour Intensity Index, it meant that the pure chemicals were dilutedat 1% in Dipropylene Glycol, odor-free solvent used in perfumery. Thispercentage is more representative of usage levels. Smelling strips, orso called “blotters”, were dipped and presented to the expert panellistfor evaluation. Expert panellists are assessors trained for at least sixmonths in odor grading and whose gradings are checked for accuracy andreproducibility versus a reference on an on-going basis. For each aminecompound, the panellist was presented two blotters: one reference (MeAnthranilate, unknown from the panellist) and the sample. The panellistwas asked to rank both smelling strips on the 0-5 odor intensity scale,0 being no odor detected, 5 being very strong odor present.

Results

The following represents Odour Intensity Index of an amine compoundsuitable for use in the present invention and according to the aboveprocedure. In each case, numbers are arithmetic averages among 5 expertpanellists and the results are statistically significantly different at95% confidence level:

Methylanthranilate 1% (reference) 3.4 Ethyl-4-aminobenzoate (EAB) 1% 0.9

A general structure for the primary amine compound of the invention isas follows:

B—(NH2)_(n);

wherein B is a carrier material, and n is an index of value of at least1.

Compounds containing a secondary amine group have a structure similar tothe above excepted that the compound comprises one or more —NH— groupsinstead of —NH2. Further, the compound structure may also have one ormore of both —NH2 and —NH— groups.

Preferred B carriers are inorganic or organic carriers.

By “inorganic carrier”, it is meant carrier which are non-orsubstantially non carbon based backbones.

Preferred primary and/or secondary amines, among the inorganic carriers,are those selected from mono or polymers or organic-organosiliconcopolymers of amino derivatised organo silane, siloxane, silazane,alumane, aluminum siloxane, or aluminum silicate compounds. Typicalexamples of such carriers are: organosiloxanes with at least oneprimary, amine moiety like the diaminoalkylsiloxane [H2NCH2(CH3) 2Si]O,or the organoaminosilane (C6H5) 3SiNH2 described in: Chemistry andTechnology of Silicone, W. Noll, Academic Press Inc. 1998, London, pp209, 106).

Preferred primary and/or secondary amines, among the organic carriers,are those selected from aminoaryl derivatives, polyamines, amino acidsand derivatives thereof, substituted amines and amides, glucamines,dendrimers, the polyvinylamines with a MW of from 600-50K; aminosubstituted polyvinylalcohol with a MW ranging from 400-300,000;polyoxyethylene bis[amine]; polyoxyethylene bis[6-aminohexyl];N,N′-bis-(3-aminopropyl)-1,3-propanediamine linear or branched;1,4-bis-(3-aminopropyl)piperazine, and mixtures thereof.

Preferred aminoaryl derivatives are the amino-benzene derivativesincluding the alkyl esters of 4-amino benzoate compounds, and morepreferably selected from ethyl-4-amino benzoate,phenylethyl-4-aminobenzoate, phenyl-4-aminobenzoate,4-amino-N′-(3-aminopropyl)-benzamide, and mixtures thereof.

Polyamines suitable for use in the present invention arepolyethyleneimines polymers, poly[oxy(methyl-1,2-ethanediyl)],α-(2-aminomethylethyl)-ω-(2-aminomethyl-ethoxy)-(=C.A.S No. 9046-10-0);poly[oxy(methyl-1,2-ethanediyl)], α-hydro-)ω-(2-aminomethylethoxy)-,ether with 2-ethyl-2-(hydroxymethyl)-1,3-propanediol (=C.A.S. No.39423-51-3); commercially available under the tradename JeffaminesT-403, D-230, D400, D-2000; 2,2′,2′-triaminotriethylamine;2,2′-diamino-diethylamine; 3,3′-diamino-dipropylamine, 1,3 bisaminoethyl-cyclohexane commercially available from Mitsibushi and theC12 Sternamines commercially available from Clariant like the C12Sternamin(propylenamine)_(n) with n=¾, and mixtures thereof. Preferredpolyamines are polyethyleneimines commercially available under thetradename Lupasol like Lupasol FG, G20,wtv, PR8515, WF, FC, G20, G351G100, HF, P, PS, SK, SNA.

Preferred amino acids for use herein are selected tyrosine, tryptophane,lysine, glutamic acid, glutamine, aspartic acid, arginine, asparagine,phenylalanine, proline, glycine, serine, histidine, threonine,methionine, and mixture thereof, most preferably selected from tyrosine,tryptophane, and mixture thereof. Preferred amino acid derivativesselected from tyrosine ethylate, glycine methylate, tryptophaneethylate, and mixture thereof.

Preferred substituted amines and amides for use herein are selected fromnipecotamide, N-coco-1,3-propenediamine; N-oleyl-1,3-propenediamine;N-(tallow alkyl)-1,3-propenediamine; 1,4-diamino cyclohexane;1,2-diamino-cyclohexane; 1,12-diaminododecane, and mixtures thereof.

Other primary amine compounds suitable for use herein are theglucamines, preferably selected from 2,3,4,5,6-pentamethoxy-glucamine;6-acetylglucamine, glucamine, and mixture thereof.

Also preferred compounds are the polyethylenimine and/orpolypropylenimine dendrimers and the commercially available Starburst®polyamidoamines (PAMAM) dendrimers, generation G0-G10 from Dendritechand the dendrimers Astromols®, generation 1-5 from DSM beingDiAminoButane PolyAmine DAB (PA)x dendrimers with x=2^(n)×4 and n beinggenerally comprised between 0 and 4.

Still other preferred primary and/or secondary amine containingcompounds are amino-functional polymers. Preferred amino-functionalpolymers for use in the present invention are selected from thepolyvinylamines, derivatives thereof, copolymer thereof, alkylenepolyamine, polyaminoacids and copolymer thereof, cross-linkedpolyaminoacids, amino substituted polyvinylalcohol, polyoxyethylene bisamine or bis aminoalkyl, aminoalkyl piperazine and derivatives,N,N′-bis-(3-aminopropyl)-1,3-propanediamine linear or branched (TPTA),and mixtures thereof.

Polyamino acid is one suitable and preferred class of amino-functionalpolymer. Polyaminoacids are compounds which are made up of amino acidsor chemically modified amino acids. They can contain alanine, serine,aspartic acid, arginine, valine, threonine, glutamic acid, leucine,cysteine, histidine, lysine, isoleucine, tyrosine, asparagine,methionine, proline, tryptophan, pheeylaranine, glutamine, glycine ormixtures thereof. In chemically modified amino acids, the amine oracidic function of the amino acid has reacted with a chemical reagent.This is often done to protect these chemical amine and acid functions ofthe amino acid in a subsequent reaction or to give special properties tothe amino acids, like improved solubility. Examples of such chemicalmodifications are benzyloxycarbonyl, aminobutyric acid, butyl ester,pyroglutamic acid. More examples of common modifications of amino acidsand small amino acid fragments can be found in the Bachem, 1996,Peptides and Biochemicals Catalog.

Preferred polyamino acids are polylysines, polyarginine, polyglutamine,polyasparagine, polyhistidine, polytryptophane or mixtures thereof. Mostpreferred are polylysines or polyamino acids where more than 50% of theamino acids are lysine, since the primary amine function in the sidechain of the lysine is the most reactive amine of all amino acids.

The preferred polyamino acid has a m molecular weight of 500 to10,000,000, more preferably between 5,000 and 750,000.

The polyamino acid can be cross linked. The cross linking can beobtained for example by condensation of the amine group in the sidechain of the amino acid like lysine with the carboxyl function on theamino acid or with protein cross linkers like PEG derivatives. The crosslinked polyamino acids still need to have free primary and/or secondaryamino groups left for reaction with the active ingredient.

The preferred cross linked polyamino acid has a molecular weight of20,000 to 10,000,000, more preferably between 200,000 and 2,000,000.

The polyamino acid or the amino acid can be co-polymerized with otherreagents like for instance with acids, amides, acyl chlorides. Morespecifically with aminocaproic acid, adipic acid, ethylhexanoic acid,caprolactam or mixture thereof. The molar ratio used in these copolymersranges from 1:1 (reagent/amino acid (lysine)) to 1:20, more preferablyfrom 1:1 to 1:10.

The polyamino acid like polylysine can be partially ethoxylated.

Examples and supply of polyaminoacids containing lysine, arginine,glutamime, asparagine are given in the Bachem 1996, Peptides andBiochemicals catalog.

The polyaminoacid can be obtained before reaction with the activeingredient, under a salt form. For example polylysine can be supplied aspolylysine hydrobromide. Polylysine hydrobromide is commerciallyavailable from Sigma, Applichem, Bachem and Fluka.

Examples of suitable amino functional polymers containing at least oneprimary and/or secondary amine group for the purpose of the presentinvention are:

Polyvinylamine with a MW of about 300-2.10 E6;

Polyvinylamine alkoxylated with a MW of about 600, 1200 or 3000 and anethoxylation degree of 0.5;

Polyvinylamine vinylalcohol—molar ratio 2:1,polyvinylaminevinylformamide—molar ratio 1:2 and polyvinylaminevinylformamide-molar ratio 2:1;

Triethylenetetramine, diethylenetriamine, tetraethylenepentamine;

Bis-aminopropylpiperazine;

Polyamino acid (L-lysine/lauric acid in a molar ratio of 10/1),Polyamino acid (L-lysine/aminocaproic acid/adipic acid in a molar ratioof 515/1),), Polyamino acid (L-lysine/aminocaproic acid/ethylhexanoicacid in a molar ratio of 5/3/1) Polyamino acid(polylysine-cocaprolactam); Polylysine hydrobromide; cross-linkedpolylysine,

amino substituted polyvinylalcohol with a MW ranging from 400-300,000;

polyoxyethylene bis[amine] available from e.g. Sigma;

polyoxyethylene bis[6-aminohexyl] available from e.g. Sigma;

N,N′-bis-(3-aminopropyl)-1,3-propanediamine linear or branched (TPTA);and

1,4-bis-(3-aminopropyl)piperazine (BNPP).

The more preferred compounds are ethyl-4-amino benzoate,polyethyleneimine polymers commercially available under the tradenameLupasol like Lupasol FG, G20, wfv, PR8515, WF, FC, G20, G35, G100, HF,P, PS, SK, SNA; glucamine; the diaminobutane dendrimers Astramol®,polyvinylamines with a MW ranging from 600, 1200, 3K, 20K, 25K or 50K;amino substituted polyvinylalcohol with a MW ranging from 400-300,000;polyoxyethylene bis[amine]; polyoxyethylene bis[6-aminohexyl];polyaminoacid, cross-linked polyaminoacid,N,N′-bis-(3-aminopropyl)-1,3-propanediamine linear or branched;1,4-bis-(3-aminopropyl)piperazine, and mixture thereof. Most preferredprimary and/or secondary amine compounds are selected from ethyl-4-aminobenzoate, polyethyleneimine polymers commercially available under thetradename Lupasol like Lupasol FG, G20,wfv, PR8515, WF, FC, G20, G35,G100, HF, P, PS, SK, SNA; the diaminobutane dendrimers Astramol®,N,N′-bis-(3-aminopropyl)-1,3-propanediamine linear or branched;1,4-bis-(3-aminopropyl)piperazine, and mixtures thereof. Even mostpreferred compounds are those selected from ethyl-4-amino benzoate,polyethyleneimine polymers commercially available under the tradenameLupasol like Lupasol FG, G20,wfv, PR8515, WF, FC, G20, G35, G100, HF, P,PS, SK, SNA; N,N′-bis-(3-aminopropyl)-1,3-propanediamine linear orbranched, 1,4-bis-(3-aminopropyl)piperazine, polylysine, cross-linkedpolylysine, and mixtures thereof.

Advantageously, such most preferred primary and/or secondary aminecompounds also provide fabric appearance benefit, in particular colourappearance benefit, thus providing a resulting amine reaction productwith the dual properties of both fabric appearance benefit and delayedrelease of the active. Further, when the primary and/or secondary aminecompound has more than one free primary and/or secondary amine group,several different active ingredients (aldehyde and/or ketone) can belinked to the amine compound.

B-Active Ketone and/or Aldehyde

Preferably, for the above mentioned compounds, by active ketone oractive aldehyde, it is meant any chain containing at least 1 carbonatom, preferably at least 5 carbon atoms.

Preferably, the active ketone or active aldehyde is respectivelyselected from a flavour ketone or aldehyde ingredient, a pharmaceuticalketone or aldehyde active, a biocontrol ketone or aldehyde agent, aperfume ketone or aldehyde component and mixtures thereof; mostpreferably a perfume ketone and/or aldehyde.

Flavour ingredients include spices, flavor enhancers that contribute tothe overall flavour perception.

Pharmaceutical actives include drugs.

Biocontrol agents include biocides, antimicrobials, bactericides,fungicides, algaecides, mildewcides, disinfectants, sanitiser likebleach, antiseptics, insecticides, insect and/or moth repellant,vermicides, plant growth hormones.

Typical antimicrobials include Glutaraldehyde, Cinnamaldehyde, andmixtures thereof. Typical insect and/or moth repellants are perfumeingredients, such as citronellal, citral, N,N diethyl meta toluamide,Rotundial, 8-acetoxycarvotanacenone, and mixtures thereof. Otherexamples of insect and/or moth repellant for use herein are disclosed inU.S. Pat. Nos. 4,449,987, 4,693,890, 4,696,676, 4,933,371, 5,030,660,5,196,200, and “Semio Activity of Flavor and Fragrance molecules onvarious Insect Species”, B. D. Mookherjee et al., published in BioactiveVolatile Compounds from Plants, ASC Symposium Series 525, R. Teranishi,R. G. Buttery, and H. Sugisawa, 1993, pp. 35-48.

A typical disclosure of suitable ketone and/or aldehydes, traditionallyused in perfumery, can be found in “perfume and Flavor Chemicals”, Vol.I and II, S. Arctander, Allured Publishing, 1994, ISBN 0-931710-35-5.

Perfume ketones components include components having odoriferousproperties.

Preferably, for the above mentioned compounds, the perfume ketone isselected from buccoxime; iso jasmone; methyl beta naphthyl ketone; muskindanone; tonalid/musk plus; Alpha-Damascone, Beta-Damascone,Delta-Damascone, Iso-Damascone, Damascenone, Damarose,Methyl-Dihydrojasmonate, Menthone, Carvone, Camphor, Fenchone,Alpha-lonone, Beta-lonone, Gamma-Methyl so-called lonone, Fleuramone,Dihydrojasmone, Cis-Jasmone, Iso-E-Super, Methyl- Cedrenyl-ketone orMethyl-Cedrylone, Acetophenone, Methyl-Acetophenone,Para-Methoxy-Acetophenone, Methyl-Beta-Naphtyl-Ketone, Benzyl-Acetone,Benzophenone, Para-Hydroxy-Phenyl-Butanone, Celery Ketone or Livescone,6-lsopropyldecahydro-2-naphtone, Dimethyl-Octenone, Freskomenthe,4-(1-Ethoxyvinyl)-3,3,5,5,-tetramethyl-Cyclohexanone, Methyl-Heptenone,2-(2-(4-Methyl-3-cyclohexen-1-yl)propyl)-cyclopentanone,1-(p-Menthen-6(2)-yl)-1-propanone,4-(4-Hydroxy-3-methoxyphenyl)-2-butanone,2-Acetyl-3,3-Dimethyl-Norbornane,6,7-Dihydro-1,1,2,3,3-Pentamethyl-4(5H)-Indanone, 4-Damascol, Dulcinylor Cassione, Gelsone, Hexalon, Isocyciemone E, Methyl Cyclocitrone,Methyl-Lavender-Ketone, Orivon, Para-tertiary-Butyl-Cyclohexanone,Verdone, Delphone, Muscone, Neobutenone, Plicatone, Veloutone,2,4,4,7-Tetramethyl-oct-6-en-3-one, Tetrameran, hedione, and mixturesthereof.

More preferably, for the above mentioned compounds, the preferredketones are selected from Alpha Damascone, Delta Damascone, IsoDamascone, Carvone, Gamma-Methyl-lonone, Iso-E-Super,2,4,4,7-Tetramethyl-oct-6-en-3-one, Benzyl Acetone, Beta Damascone,Damascenone, methyl dihydrojasmonate, methyl cedrylone, hedione, andmixtures thereof.

Perfume aldehyde components include components having odoriferousproperties.

Preferably, for the above mentioned compounds, the perfume aldehyde isselected from adoxal; anisic aldehyde; cymal; ethyl vanillin;florhydral; helional; heliotropin; hydroxycitronellal; koavone; lauricaldehyde; lyral; methyl nonyl acetaldehyde; P. T. bucinal; phenylacetaldehyde; undecylenic aldehyde; vanillin;2,6,10-trimethyl-9-undecenal, 3-dodecen-1-al, alpha-n-amyl cinnamicaldehyde, 4-methoxybenzaldehyde, benzaldehyde, 3-(4-tertbutylphenyl)-propanal, 2-methyl-3-(para-methoxyphenyl propanal,2-methyl-4-(2,6,6-trimethyl-2(1)-cyclohexen-1-yl)butanal,3-phenyl-2-propenal, cis-/trans-3,7-dimethyl-2,6-octadien-1-al,3,7-dimethyl-6-octen-1-al, [(3,7dimethyl-6-octenyl)oxy]acetaldehyde,4-isopropylbenzyaldehyde,1,2,3,4,5,6,7,8-octahydro-8,8-dimethyl-2-naphthaldehyde,2,4-dimethyl-3-cyclohexen-1-carboxaldehyde,2-methyl-3-(isopropylphenyl)propanal, 1-decanal; decyl aldehyde,2,6-dimethyl-5-heptenal,4-(tricyclo[5.2.1.0(2,6)]-decylidene-8)-butanal,octahydro-4,7-methano-1H-indenecarboxaldehyde, 3-ethoxy-4-hydroxybenzaldehyde, para-ethyl-alpha, alpha-dimethyl hydrocinnamaldehyde,alpha-methyl-3,4-(methylenedioxy)hydrocinnamaldehyde,3,4-methylenedioxybenzaldehyde, alpha-n-hexyl cinnamic aldehyde,m-cymene-7-carboxaldehyde, alpha-methyl phenyl acetaldehyde,7-hydroxy-3,7-dimethyl octanal, Undecenal,2,4,6-trimethyl-3-cyclohexene-1-carboxaldehyde,4-(3)(4-methyl-3-pentenyl)-3-cyclohexen-carboxaldehyde, 1-dodecanal,2,4-dimethyl cyclohexene-3-carboxaldehyde, 4-(4-hydroxy-4-methylpentyl)-3-cylohexene-1-carboxaldehyde, 7-methoxy-3,7-dimethyloctan-1-al,2-methyl undecanal, 2-methyl decanal, 1-nonanal, 1-octanal,2,6,10-trimethyl-5,9-undecadienal, 2-methyl-3-(4-tertbutyl)propanal,dihydrocinnamic aldehyde,1-methyl-4-(4-methyl-3-pentenyl)-3-cyclohexene-1-carboxaldehyde, 5 or 6methoxyOhexahydro-4,7-methanoindan-1 or 2-carboxaldehyde,3,7-dimethyloctan-1-al, 1-undecanal, 10-undecen-1-al,4-hydroxy-3-methoxy benzaldehyde, 1-methyl-3-(4-methylpentyl)-3-cyclhexenecarboxaldehyde,7-hydroxy-3,7-dimethyl-octanal, trans-4-decenal, 2,6-nonadienal,para-tolyfacetaldehyde; 4-methylphenylacetaldehyde,2-methyl-4-(2,6,6-trimethyl-1-cyclohexen-1-yl)-2-butenal,ortho-methoxycinnamic aldehyde, 3,5,6-trimethyl-3-cyclohexenecarboxaldehyde, 3,7-dimethyl-2-methylene-6-octenal, phenoxyacetaldehyde,5,9-dimethyl-4,8-decadienal, peonyaldehyde(6,10-dimethyl-3-oxa-5,9-undecadien-1-al),hexahydro-4,7-methanoindan-1-carboxaldehyde, 2-methyl octanal,alpha-methyl-4-(1-methyl ethyl)benzene acetaldehyde,6,6-dimethyl-2-norpinene-2-propionaldehyde, para methyl phenoxyacetaldehyde, 2-methyl-3-phenyl-2-propen-1-al, 3,5,5-trimethyl hexanal,Hexahydro-8,8-dimethyl-2-naphthaldehyde,3-propyl-bicyclo[2.2.1]hept-5-ene-2-carbaldehyde, 9-decenal,3-methyl-5-phenyl-1-pentanal, methyinonyl acetaldehyde,1-p-menthene-q-carboxaldehyde, citral, lilial and mixtures thereof.

Most preferred aldehydes are selected from citral, 1-decanal,benzaldehyde, florhydral, 2,4-dimethyl-3-cyclohexen-1-carboxaldehyde;cis/trans-3,7-dimethyl-2,6-octadien-1-al; heliotropin;2,4,6-trimethyl-3-cyclohexene-1-carboxaldehyde; 2,6-nonadienal;alpha-n-amyl cinnamic aldehyde, alpha-n-hexyl cinnamic aldehyde, P. T.Bucinal, lyral, cymal, methyl nonyl acetaldehyde, trans-2-nonenal,lilial, trans-2-nonenal, and mixture thereof.

In the above list of perfume ingredients, some are commercial namesconventionally known to one skilled in the art, and also includesisomers. Such isomers are also suitable for use in the presentinvention.

In another embodiment, especially suitable for the purpose of thepresent invention are the perfume compounds, preferably the perfumeketones or aldehydes, characterised by having a low Odor DetectionThreshold. Such Odor Detection Threshold (ODT) should be lower than 1ppm, preferably lower than 10 ppb—measured at controlled GasChromatography (GC) conditions such as described here below. Thisparameter refers to the value commonly used in the perfumery arts andwhich is the lowest concentration at which significant detection takesplace that some odorous material is present. Please refer for example in“Compilation of Odor and Taste Threshold Value Data (ASTM DS 48 A)”,edited by F. A. Fazzalari, International Business Machines, HopwellJunction, N.Y. and in Calkin et al., Perfumery, Practice and Principles,John Willey & Sons, Inc., page 243 et seq (1994). For the purpose of thepresent invention, the Odor Detection Threshold is measured according tothe following method: The gas chromatograph is characterized todetermine the exact volume of material injected by the syringe, theprecise split ratio, and the hydrocarbon response using a hydrocarbonstandard of known concentration and chain-length distribution. The airflow rate is accurately measured and, assuming the duration of a humaninhalation to last 0.02 minutes, the sampled volume is calculated. Sincethe precise concentration at the detector at any point in time is known,the mass per volume inhaled is known and hence the concentration ofmaterial. To determine the ODT of a perfume material, solutions aredelivered to the sniff port at the back-calculated concentration. Apanelist sniffs the GC effluent and identifies the retention time whenodor is noticed. The average over all panelists determines the thresholdof noticeability. The necessary amount of analyte is injected onto thecolumn to achieve a certain concentration, such as 10 ppb, at thedetector. Typical gas chromatograph parameters for determining odordetection thresholds are listed below.

GC: 5890 Series II with FID detector

7673 Autosampler

Column: J&W Scientific DB-1

Length 30 meters ID 0.25 mm film thickness 1 micron

Method:

Split Injection: 17/1 split ratio

Autosampler: 1.13 microliters per injection

Column Flow: 1.10 mL minute

Air Flow: 345 mL/minute

Inlet Temp. 245° C.

Detector Temp. 285° C.

Temperature Information

Initial Temperature: 50° C.

Rate: 5 C./minute

Final Temperature: 280° C.

Final Time: 6 minutes

Leading assumptions: 0.02 minutes per sniff

GC air adds to sample dilution

Examples of such preferred perfume components are those selected from:2-methyl-2-(para-iso-propylphenyl)-propionaldehyde,1-(2,6,6-trimethyl-2-cyclohexan-1-yl)-2-buten-1-one and/orpara-methoxy-acetophenone. Even more preferred are the followingcompounds having an ODT≦10 ppb measured with the method described above:undecylenic aldehyde, undecalactone gamma, heliotropin, dodecalactonegamma, p-anisic aldehyde, para hydroxy-phenyl-butanone, cymal, benzylacetone, ionone alpha, p.t.bucinal, damascenone, ionone beta andmethyl-nonyl ketone.

Typically the level of active is of from 10 to 90%, preferably from 30to 85%, more preferably from 45 to 80% by weight of the amine reactionproduct.

Preferred amine reaction products are those which have a Dry SurfaceOdour Index as per given in co-pending application EP 98870155.3 givenat page 29, line 26 to page 32 line 29, in which the specifiedunperfumed base for fabric surfaces and hard surfaces are respectivelyas follow:

% by weight Composition for fabric surface test LAS 16 NaSKS-6 6 PB1 8TAED 2.4 Carbonate 1 Sodium Carbonate 1 HEDP 0.4 SRP1 0.2 Photobleach0.013 Citric acid 1.0 Protease 0.3 Lipase 0.1 Cellulase 0.1 Amylase 0.3Zeolilte 3.0 TFAA 3.0 QAS1 2.5 Silicone antifoam 1.0 Misc/minors tobalance to 100% Composition for hard surface test C12-14 EO 21 2 C12-14EO 5 2.5 C9-11 EO 5 2.5 LAS 0.8 Na2CO3 0.2 Citric acid 0.8 Caustic acid0.5 Fatty acid 0.5 SCS 1.5 Water &Misc/Minors to balance to 100%

Most preferred amine reaction products are those resulting from thereaction of polyethyleneimine polymer like Lupasol polymers, BNPP, orTPTA with one or more of the following Alpha Damascone, Delta Damascone,Carvone, Gamma-Methyl-lonone, Hedione, Florhydral, Lilial, Heliotropine,and 2,4-dimethyl-3-cyclohexen-1-carboxaldehyde. Still other preferredamine reaction products are those resulting from the reaction ofAstramol Dendrimers with Carvone as well as those resulting from thereaction of ethyl-4-amino benzoate with one or more of the following2,4-dimethyl-3-cyclohexen-1-carboxaldehyde, and trans-2-nonenal. Stillanother preferred amine reaction products are those resulting from thereaction of polylysine with one or more of the following AlphaDamascone, Delta Damascone, Carvone, and2,4-dimethyl-3-cyclohexen-1-carboxaldehyde.

Even most preferred amine reaction products are those from the reactionof Lupasol HF with Delta Damascone; LupasolG35 with Alpha Damascone;LupasolG100 with 2,4dimethyl-3-cyclohexen-1-carboxaldehyde, BNPP or TPTAwith Alpha and Delta Damascone; ethyl4-amino benzoate with2,4-dimethyl-3-cyclohexen-1-carboxaldehyde.

2)-Carrier

Another essential ingredient of the process invention is a carrierhaving a melting point between 30° C. and 135° C., preferably between45° C. and 85° C. By means of this carrier, particles of amine reactionproduct will be produced.

Suitable carrier for use in the process invention are components likeorganic polymeric compounds, waxes, paraffins, oils, glycerides,monoglycerides, diglycerides, triglycerides, anionic surfactants;nonionic surfactants, cationic surfactants, zwitterionic surfactants,and mixtures thereof, preferably selected from organic polymericcompound, nonionic surfactants, and mixtures thereof.

Preferred organic polymeric compounds suitable for mixing with primaryand/or secondary amine compound herein include polyethylene glycols, andderivatives thereof, particularly those of molecular weight 1000-10000,more particularly 2000 to 8000 and most preferably about 4000.

Essentially any nonionic surfactants useful for detersive purposes canbe included in the compositions provided it has a melting point between30° C. and 135° C.

Exemplary, non-limiting classes of useful nonionic surfactants arelisted below.

Nonionic Polyhydroxy Fatty Acid Amide Surfactant

Polyhydroxy fatty acid amides suitable for use herein are those havingthe structural formula R2CONR1Z wherein : R1 is H, C₁-C₄ hydrocarbyl,2-hydroxy ethyl, 2-hydroxy propyl, or a mixture thereof, preferableC1-C4 alkyl, more preferably C₁ or C₂ alkyl, most preferably C₁ alkyl(i.e., methyl); and R2 is a C₅-C₃₁ hydrocarbyl, preferablystraight-chain C₅-C₁₉ alkyl or alkenyl, more preferably straight-chainC₉-C₁₇ alkyl or alkenyl, most preferably straight-chain C₁₁-C₁₇ alkyl oralkenyl, or mixture thereof; and Z is a polyhydroxyhydrocarbyl having alinear hydrocarbyl chain with at least 3 hydroxyls directly connected tothe chain, or an alkoxylated derivative (preferably ethoxylated orpropoxylated) thereof. Z preferably will be derived from a reducingsugar in a reductive amination reaction; more preferably Z is aglycityl.

Nonionic Condensates of Alkyl Phenols

The polyethylene, polypropylene, and polybutylene oxide condensates ofalkyl phenols are suitable for use herein. In general, the polyethyleneoxide condensates are preferred. These compounds include thecondensation products of alkyl phenols having an alkyl group containingfrom about 6 to about 18 carbon atoms in either a straight chain orbranched chain configuration with the alkylene oxide with from about 1to about 150 moles of alkylene oxide per mole of alcohol.

Nonionic Ethoxylated Alcohol Surfactant

The alkyl ethoxylate condensation products of aliphatic alcohols withfrom about 1 to about 150 moles of ethylene oxide are suitable for useherein. The alkyl chain of the aliphatic alcohol can either be straightor branched, primary or secondary, and generally contains from 6 to 22carbon atoms. Particularly preferred are the condensation products ofalcohols having an alkyl group containing from 8 to 20 carbon atoms withfrom about 25 to about 150 moles of ethylene oxide per mole of alcohol,preferably 50 to 100, more preferably 80 moles of ethylene oxide permole of alcohol.

Preferred nonionic ethoxylated alcohol surfactants are selected fromtallow (C₁₆-C₁₈) alcohol ethoxylated with 25, 50, 80, or 100 moles ofethylene oxide commercially available from under the tradename ofLutensol from BASF, Empilan from Albright and Wilson, and Genapol fromClariant. The most preferred nonionic ethoxylated alcohol surfactant istallow (C₁₆-C₁₈) alcohol ethoxylated with 80 moles of ethylene oxide andcommercially available under the tradename of Lutensol 80/80 from BASF,Empilan KM 80 from Albright and Wilson, or Genapol T800 from Clariant.

Nonionic Ethoxylated/Propoxylated Fatty Alcohol Surfactant

The ethoxylated C₆-C₂₂ fatty alcohols and C₆-C₂₂ mixedethoxylated/propoxylated fatty alcohols are suitable surfactants for useherein, particularly where water soluble. Preferably the ethoxylatedfatty alcohols are the C₁₀-C₂₂ ethoxylated fatty alcohols with a degreeof ethoxylation of from 25 to 150, most preferably these are the C₁₂-C₁₈ethoxylated fatty alcohols with a degree of ethoxylation from 50 to 80.Preferably the mixed ethoxylated/propoxylated fatty alcohols have analkyl chain length of from 10 to 18 carbon atoms, a degree ofethoxylation of from 3 to 30 and a degree of propoxylation of from 1 to30.

Nonionic EO/PO Condensates with Propylene Glycol

The condensation products of ethylene oxide with a hydrophobic baseformed by the condensation of propylene oxide with propylene glycol aresuitable for use herein. The hydrophobic portion of these compoundspreferably has a molecular weight of from about 1500 to about 1800 andexhibits water insolubility. Examples of compounds of this type includecertain of the commercially-available Pluronic™ surfactants, marketed byBASF.

Nonionic EO Condensation Products with Propylene Oxide/Ethylene DiamineAdducts

The condensation products of ethylene oxide with the product resultingfrom the reaction of propylene oxide and ethylenediamine are suitablefor use herein. The hydrophobic moiety of these products consists of thereaction product of ethylenediamine and excess propylene oxide, andgenerally has a molecular weight of from about 2500 to about 3000.Examples of this type of nonionic surfactant include certain of thecommercially available Tetronic™ compounds, marketed by BASF.

Nonionic Alkylrolysaccharide Surfactant

Suitable alkylpolysaccharides for use herein are disclosed in U.S. Pat.No. 4,565,647, Llenado, issued Jan. 21, 1986, having a hydrophobic groupcontaining from about 6 to about 30 carbon atoms, preferably from about10 to about 16 carbon atoms and a polysaccharide, e.g., a polyglycoside,hydrophilic group containing from about 1.3 to about 10, preferably fromabout 1.3 to about 3, most preferably from about 1.3 to about 2.7saccharide units. Any reducing saccharide containing 5 or 6 carbon atomscan be used, e.g., glucose, galactose and galactosyl moieties can besubstituted for the glucosyl moieties. (Optionally the hydrophobic groupis attached at the 2-, 3-, 4-, etc. positions thus giving a glucose orgalactose as opposed to a glucoside or galactoside.) The intersaccharidebonds can be, e.g., between the one position of the additionalsaccharide units and the 2-, 3-, 4-, and/or 6-positions on the precedingsaccharide units.

The preferred alkylpolyglycosides have the formula

R2O((CnH2n)O)t(glycosyl)_(x)

wherein R2 is selected from the group consisting of alkyl, alkylphenyl,hydroxyalkyl, hydroxyalkylphenyl, and mixtures thereof in which thealkyl groups contain from 10 to 18, preferably from 12 to 14, carbonatoms; n is 2 or 3; t is from 0 to 10, preferably 0, and X is from 1.3to 8, preferably from 1.3 to 3, most preferably from 1.3 to 2.7. Theglycosyl is preferably derived from glucose.

Nonionic Fatty Acid Amide Surfactant

Fatty acid amide surfactants suitable for use herein are those havingthe formula: R⁶CON(R⁷)₂ wherein R⁶ is an alkyl group containing from 7to 21, preferably from 9 to 17 carbon atoms and each R⁷ is selected fromthe group consisting of hydrogen, C₁-C₄ alkyl, C₁-C₄ hydroxyalkyl, and—(C₂H₂O)_(x)H, where x is in the range of from 1 to 3.

Preferred carrier materials are selected from nonionic ethoxylatedalcohol surfactants.

Typically when the amine reaction product is only mixed with a carrierbut not further processed, the amine reaction product will be present inan amount of from 1 to 75%, preferably 10 to 60%, more preferably 15 to45% by weight of the processed reaction product in the producedparticle. In this instance, the amount of carrier will be sufficient toadd up to 100%. Of course, the particle may also contain minors but inquantities which will not exceed the amount of carrier material.Typically the carrier will be present in an amount of from 3 to 95%,preferably from 15 to 80% and most preferably from 25 to 75%, by weightof the produced particles in the processed amine reaction product.

Processing of the amine reaction product with the carrier is done bythoroughly mixing the amine reaction product with the carrier.Advantageously, there is no need for additional ingredients to provide aresulting substantially homogenous mixture. This mixing is done at thelowest possible temperature, i.e. just above the melting point of thecarrier. The mixing step is carried out until a complete homogeneousmixture is obtained. By “homogeneous”, it is meant compositions whichhave similar appearance to the resulting composition of a 20 g of aminereaction product mixed with 80 g of TAE80 for 5 minutes by means of anUltra Turrax, the temperature of mixing being of about 70° C.

Coating Agents

When use of a carrier with a melting point between 35 and 135° C. ismade for the mixing with the amine reaction product, it is thenpreferred to further process the mixture to form a coated particle likee.g. by adsorption of the mixture onto a solid, preferably porouscoating. The resulting coated particles can be in any form which issuitable for incorporation into liquid or powders, preferably powders,such as agglomerate, pellets, tablets, or mixtures thereof.

Suitable coating agents for both solid, including paste, and liquidmixture are substantially water-soluble solid binder or agglomeratingagents.

“Substantially water soluble” shall refer to a material that is solublein distilled (or equivalent) water, at 25° C., at a concentration of0.2% by weight, and are preferably soluble at 1.0% by weight.

A “solid” is defined as a material that is a solid at ambienttemperatures, and so solid substantially water-soluble binder oragglomerating agent must have a melting point of at least 30° C., andpreferably of at least 40° C.

Suitable water-soluble binders or agglomerating agents include the watersoluble organic polymeric compounds, water soluble monomericpolycarboxylates, or their acid forms, homo or copolymericpolycarboxylic acids or their salts in which the polycarboxylic acidcomprises at least two carboxylic radicals separated from each other bynot more that two carbon atoms, carbonates, bicarbonates, borates,phosphates, sulfate salts like sodium and magnesium sulfate, inorganicperhydrate salts including perborate like perborate monohydrate,percarbonate, silicates, starch, cyclodextrin, and mixtures of any ofthe foregoing.

Suitable organic polymeric compounds suitable as coating agents includecellulose derivatives such as methylcellulose, carboxymethylcellulose,hydroxypropyicellulose and hydroxyethyicellulose, as well ascarbohydrates like pectins, and gums. Further compounds arecarbohydrates and derivatives such as fructose, xylose, galactose,galacturonic acid or glucose based polymers like inuline, dextran,xyloglucan, pectin or gums.

Suitable carboxylates containing one carboxy group include the watersoluble salts of lactic acid, glycolic acid and ether derivativesthereof. Polycarboxylates containing two carboxy groups include thewater-soluble salts of succinic acid, malonic acid, (ethylenedioxy)diacetic acid, maleic acid, diglycolic acid, tartaric acid, tartronicacid and fumaric acid, as well as the ether carboxylates and thesulfinyl carboxylates. Polycarboxylates containing three carboxy groupsinclude, in particular, water-soluble citrates, aconitrates andcitraconates as well as succinate derivatives such as thecarboxymethyloxysuccinates described in British Patent No. 1,379,241,lactoxysuccinates described in British Patent No. 1,389,732, andaminosuccinates described in Netherlands Application 7205873, and theoxypolycarboxylate materials such as 2-oxa-1,1,3-propane tricarboxylatesdescribed in British Patent No. 1,387,447.

Polycarboxylates containing four carboxy groups include oxydisuccinatesdisclosed in British Patent No. 1,261,829, 1,1,2,2-ethanetetracarboxylates, 1,1,3,3-propane tetracarboxylates and 1,1,2,3-propanetetracarboxylates. Polycarboxylates containing sulfo substituentsinclude the sulfosuccinate derivatives disclosed in British Patent Nos.1,398,421 and 1,398,422 and in U.S. Pat. No. 3,936,448, and thesulfonated pyrolysed citrates described in British Patent No. 1,439,000.

Alicyclic and heterocyclic polycarboxylates includecyclopentane-cis,cis,cis-tetracarboxylates, cyclopentadienidepentacarboxylates,2,3,4,5-tetrahydrofuran-cis,cis,cis-tetracarboxylates,2,5-tetrahydrofuran-cis-dicarboxylates,2,2,5,5-tetrahydrofuran-tetracarboxylates,1,2,3,4,5,6-hexane-hexacarboxylates and carboxymethyl derivatives ofpolyhydric alcohols such as sorbitol, mannitol and xylitol. Aromaticpolycarboxylates include mellitic acid, pyromellitic acid and thephthalic acid derivatives disclosed in British Patent No. 1,425,343.

Of the above, the preferred polycarboxylates are hydroxycarboxylatescontaining up to three carboxy groups per molecule, more particularlycitrates.

Borate, as well as builders containing boratenorming materials that canproduce borate under detergent storage or wash conditions can also beused but are not preferred at wash conditions less that about 50° C.,especially less than about 40° C.

Examples of carbonates are the alkaline earth and alkali metalcarbonates, including sodium carbonate and sesqui-carbonate and mixturesthereof with ultra-fine calcium carbonate as disclosed in German PatentApplication No. 2,321,001 published on Nov. 15, 1973.

Specific examples of water-soluble phosphates are t he alkali metaltripolyphosphates, sodium, potassium and ammonium pyrophosphate, sodiumand potassium and ammonium pyrophosphate, sodium and potassiumorthophosphate, sodium polymeta/phosphate in which the degree ofpolymerization ranges from about 6 to 21, and salts of phytic acid.

Suitable silicates include the water soluble sodium silicates with anSiO₂:Na₂O ratio of from 1.0 to 2.8, with ratios of from 1.6 to 2.4 beingpreferred, and 2.0 ratio being most preferred. The silicates may be inthe form of either the anhydrous salt or a hydrated salt. Sodiumsilicate with an SiO₂:Na₂O ratio of 2.0 is the most preferred silicate.

Typical disclosure of cyclodextrin derivatives are disclosed inWO96/05358, U.S. Pat. No: 3,426,011, Parmerter et al., issued Feb. 4,1969; U.S. Pat. Nos. 3,453,257; 3,453,258; 3,453,259; and 3,453,260, allin the names of Parmerter et al., and all issued Jul. 1, 1969; U.S. Pat.No. 3,459,731, Gramera et al., issued Aug. 5, 1969; U.S. Pat. No.3,553,191, Parmerter et al., issued Jan. 5, 1971; U.S. Pat. No.3,565,887, Parmerter et al., issued Feb. 23, 1971; U.S. Pat. No.4,535,152, Szejtli et al., issued Aug. 13, 1985; U.S. Pat. No.4,616,008, Hirai et al., issued Oct. 7, 1986; U.S. Pat. No. 4,678,598,Ogino et al., issued Jul. 7, 1987; U.S. Pat. No. 4,638,058, Brandt etal., issued Jan. 20, 1987; and U.S. Pat. No. 4,746,734, Tsuchiyama etal., issued May 24, 1988; all of said patents being incorporated hereinby reference.

Although less preferred for use herein because of their lowersolubility, partially water soluble coating agents may also be used ascoating agent. These compounds are indeed less preferred because duringthe wash cycle the amine reaction product will still be at leastpartially coated and therefore can not display its full functionality oflong lasting freshness on dry fabrics or hard surfaces. Examples ofpartially water soluble coating agents include the crystalline layeredsilicates. Examples of largely water insoluble builders include thesodium aluminosilicates.

Crystalline layered sodium silicates have the general formula

NaMSi_(x)O_(x+1.y)H₂O

wherein M is sodium or hydrogen, x is a number from 1.9 to 4 and y is anumber from 0 to 20. Crystalline layered sodium silicates of this typeare disclosed in EP-A-0164514 and methods for their preparation aredisclosed in DE-A-3417649 and DE-A-3742043. For the purpose of thepresent invention, x in the general formula above has a value of 2, 3 or4 and is preferably 2. The most preferred material is δ-Na₂Si₂O₅,available from Hoechst AG as NaSKS-6.

Suitable aluminosilicate zeolites have the unit cell formulaNa_(z)[(AlO₂)_(z)(SiO₂)_(y)]. XH₂O wherein z and y are at least 6; themolar ratio of z to y is from 1.0 to 0.5 and x is at least 5, preferablyfrom 7.5 to 276, more preferably from 10 to 264. The aluminosilicatematerial are in hydrated form and are preferably crystalline, containingfrom 10% to 28%, more preferably from 18% to 22% water in bound form.

The aluminosilicate ion exchange materials can be naturally occurringmaterials, but are preferably synthetically derived. Syntheticcrystalline aluminosilicate ion exchange materials are available underthe designations Zeolite A, Zeolite B, Zeolite P, Zeolite X, ZeoilteMAP, Zeolite HS and mixtures thereof. Zeolite A has the formula

Na₁₂[AlO₂)₁₂(SiO₂)₁₂]. xH₂O

wherein x is from 20 to 30, especially 27. Zeolite X has the formula

Na₈₆[(AlO₂)₈₆(SiO₂)₁₀₆].276H₂O.

Typically when the amine reaction product is mixed with a carrier and further processed to form a coated particle, the amine reaction productwill be present in an amount of from 1 to 75%, preferably 5 to 30%, morepreferably 6 to 25% by weight of the processed reaction product in theproduced particle.

Typically the coating agent will be present in an amount of from 10% to95%, preferably from 30 to 90%, more preferably, 50 to 75% by weight ofthe particle of the processed amine reaction product. In this instance,the amount of carrier will be sufficient to add up to 100%. Of course,the coated particle may also contain minors but in quantities which willnot exceed either of the amount of carrier material or coating agent.

Preferred coating materials are selected from carbonate, starch,cyclodextrin, and mixtures thereof.

The surface treatment of the particle can be carried out in a number ofways using equipment known in the art and the process may take in batchwise or continuous fashion.

One method for applying the coating material involves agglomeration. Anyconventional agglomerator/mixer may be used including, but not limitedto pan, rotary drum and vertical blender types. Molten coatingcompositions may also be applied either by being poured onto, or sprayatomized onto a moving bed of the mixture of amine reaction product withcarrier.

Another method for applying the coating is to pour the obtained mixture(so-called particle), as herein before described, onto the coatingmaterial and agglomerate it in a Braun Mixer. Care is also taken thatthe temperature during the mixing and/or coating step does notsubstantially exceed the melting point of the carrier material. Forexample, 150 g of a mixture containing TAEBO and 20% of the aminereaction product is poured at 60° C. into a Braun Mixer containing 300 gof carbonate. The mixing of the ingredients is carried out for about 5minutes. Care is also taken that the temperature during the coating doesnot exceed 65° C. The agglomerated particle can then be used as is forincorporation into the finished composition.

Accordingly, there is provided a processed amine reaction product asobtainable by the process of the invention.

If desired, the coated particle may also contain one or more additionalingredients like a surfactant for improved solubility or dispersability.Typical of such surfactant are the anionic, nonionic, or cationicsurfactants, a cationic, anion or non-ionic surfactant like. Preferably,the weight ratio of such additional ingredient(s) to the coating agentis of up to 1:1.

In another preferred marketing execution, an additional coating on thecoated particle can be provided, which depending on the nature of thisadditional coating will give improved storage stability, flowabilityand/or improved fabric substantivity of the coated particle. One typicalexample is polyvinyl alcohol.

Incorporation Into Finished Composition

The finished compositions aspect of the invention, including laundrycompositions, hard surface cleaning compositions, personal cleaningcompositions, comprises the incorporation of the hereinbefore describedprocessed amine reaction product together with one or more laundry orcleaning ingredient in a finished composition.

As mentioned hereinbefore, the incorporation of the processed aminereaction product is conveniently made depending on its end form byeither by spraying when in sprayable liquid form, or dry-addition whenin coated form.

Laundry compositions encompass laundry detergent compositions, includingliquid, solid form like powdered, tablets as well as softeningcompositions including rinse added softening composition as well asdryer added softening compositions.

A conventional disclosure of softening ingredients to be used in thesoftening composition of the invention can be found in EP 98870227.0,incorporated herein by reference.

Preferably, the finished composition is a detergent composition, morepreferably in solid form.

Finished compositions incorporating the processed amine reaction productwill normally contain from 0.1 to 25%, more preferably from 0.2 to 10%,and most preferably from 0.5 to 5% of the processed product on acomposition weight basis.

The preferred detergent composition, embodiment of the invention, will,preferably contain a bleach precursor, a source of alkaline hydrogenperoxide necessary to form a peroxyacid bleaching species in the washsolution and preferably will also contain other components conventionalin detergent compositions. Thus, preferred detergent compositions willincorporate one or more of surfactants, organic and inorganic builders,soil suspending and anti-redeposition agents, suds suppressors, enzymes,fluorescent whitening agents, photoactivated bleaches, perfumes,colours, clay softening agent, effervescent, and mixtures thereof.

Typical disclosure of such components can be found in EP-A-0,659,876 andEuropean patent application No. 98870226.2 which are both incorporatedherein by reference.

Clay

The compositions of the invention may preferably contain a clay,preferably present at a level of from 0.05% to 40%, more preferably from0.5% to 30%, most preferably from 2% to 20% by weight of thecomposition. For clarity, it is noted that the term clay mineralcompound, as used herein, excludes sodium aluminosilicate zeolitebuilder compounds, which however, may be included in the compositions ofthe invention as optional components.

One preferred clay may be a bentonite clay. Highly preferred aresmectite clays, as for example disclosed in the U.S. Pat. Nos. 3,862,0583,948,790, 3,954,632 and 4,062,647 and European Patents No.sEP-A-299,575 and EP-A-313,146 all in the name of the Procter and GambleCompany.

The term smectite clays herein includes both the clays in whichaluminium oxide is present in a silicate lattice and the clays in whichmagnesium oxide is present in a silicate lattice. Smectite clays tend toadopt an expandable three layer structure.

Specific examples of suitable smectite clays include those selected fromthe classes of the montmorillonites, hectorites, volchonskoites,nontronites, saponites and sauconites, particularly those having analkali or alkaline earth metal ion within the crystal lattice structure.Sodium or calcium montmorillonite are particularly preferred.

Suitable smectite clays, particularly montmorillonites, are sold byvarious suppliers including English China Clays, Laviosa, Georgia Kaolinand Colin Stewart Minerals.

Clays for use herein preferably have a particle dimension of from 10 nmto 800 nm more preferably from 20 nm to 500 mm, most preferably from 50nm to 200 mm.

Particles of the clay mineral compound may be included as components ofagglomerate particles containing other detergent compounds. Wherepresent as such components, the term “largest particle dimension” of theclay mineral compound refers to the largest dimension of the claymineral component as such, and not to the agglomerated particle as awhole.

Substitution of small cations, such as protons, sodium ions, potassiumions, magnesium ions and calcium ions, and of certain organic moleculesincluding those having positively charged functional groups cantypically take place within the crystal lattice structure of thesmectite clays. A clay may be chosen for its ability to preferentiallyabsorb one cation type, such ability being assessed by measurements ofrelative ion exchange capacity. The smectite clays suitable hereintypically have a cation exchange capacity of at least 50 meq/100 g. U.S.Pat. No. 3,954,632 describes a method for measurement of cation exchangecapacity.

The crystal lattice structure of the clay mineral compounds may have, ina preferred execution, a cationic fabric softening agent substitutedtherein. Such substituted clays have been termed ‘hydrophobicallyactivated’ clays. The cationic fabric softening agents are typicallypresent at a weight ratio, cationic fabric softening agent to clay, offrom 1:200 to 1:10, preferably from 1:100 to 1:20. Suitable cationicfabric softening agents include the water insoluble tertiary amines ordilong chain amide materials as disclosed in GB-A-1 514 276 and EP-B-0011 340.

A preferred commercially available “hydrophobically activated” clay is abentonite clay containing approximately 40% by weight of a dimethylditallow quaternary ammonium salt sold under the tradename Claytone EMby English China Clays International.

In a highly preferred embodiment of the invention, the clay is presentin an intimate mixture or in a particle with a humectant and ahydrophobic compound, preferably a wax or oil, such as paraffin oil.Preferred humectants are organic compounds, including propylene glycol,ethylene glycol, dimers or trimers of glycol, most preferably glycerol.The particle is preferably an agglomerate. Alternatively, the particlemay be such that the wax or oil and optionally the humectant form anencapsulate on the clay or alternatively, the clay be a encapsulate forthe wax or oil and the humectant. It may be preferred that the particlecomprises an organic salt or silica or silicate.

However, in another embodiment of the invention, the clay is preferablymixed with one or more surfactants and optionally builders andoptionally water, in which case the mixture is preferably subsequentlydried. Preferably, such a mixture is further processed in a spray-dryingmethod to obtain a spray dried particle comprising the clay.

It may be preferred that the flocculating agent is also comprised in theparticle or granule comprising the clay.

It may also be preferred that the intimate mixture comprises a chelatingagent.

Flocculating Agent

The compositions of the invention may contain a clay flocculating agent,preferably present at a level of from 0.005% to 10%, more preferablyfrom 0.05% to 5%, most preferably from 0.1% to 2% by weight of thecomposition.

The clay flocculating agent functions such as to bring together theparticles of clay compound in the wash solution and hence to aid theirdeposition onto the surface of the fabrics in the wash. This functionalrequirement is hence different from that of clay dispersant compoundswhich are commonly added to laundry detergent compositions to aid theremoval of clay soils from fabrics and enable their dispersion withinthe wash solution.

Preferred as clay flocculating agents herein are organic polymericmaterials having an average weight of from 100,000 to 10,000,000,preferably from 150,000 to 5,000,000, more preferably from 200,000 to2,000,000.

Suitable organic polymeric materials comprise homopolymers or copolymerscontaining monomeric units selected from alkylene oxide, particularlyethylene oxide, acrylamide, acrylic acid, vinyl alcohol, vinylpyrrolidone, and ethylene imine. Homopolymers of, on particular,ethylene oxide, but also acrylamide and acrylic acid are preferred.

European Patents No.s EP-A-299,575 and EP-A-313,146 in the name of theProcter and Gamble Company describe preferred organic polymeric clayflocculating agents for use herein.

The weight ratio of clay to the flocculating polymer is preferably from1000:1 to 1:1, more preferably from 500:1 to 1:1, most preferably from300:1 to 1:1, or even more preferably from 80:1 to 10:1, or in certainapplications even from 60:1 to 20:1.

Inorganic clay flocculating agents are also suitable herein, typicalexamples of which include lime and alum.

The flocculating agent is preferably present in a detergent base granulesuch as a detergent agglomerate, extrudate or spray-dried particle,comprising generally one or more surfactants and builders.

Effervescent

Effervescent means may also be optionally used in the compositions ofthe invention.

Effervescency as defined herein means the evolution of bubbles of gasfrom a liquid, as the result of a chemical reaction between a solubleacid source and an alkali metal carbonate, to produce carbon dioxidegas, i.e.

C₆H₈O₇+3NaHCO₃→Na₃C₆H₅O₇+3CO₂↑+3H₂O

Further examples of acid and carbonate sources and other effervescentsystems may be found in : (Pharmaceutical Dosage Forms: Tablets Volume 1Page 287 to 291).

Carbonate Salts

Suitable alkali and/or earth alkali inorganic carbonate salts hereininclude carbonate and hydrogen carbonate of potassium, lithium, sodium,and the like amongst which sodium and potassium carbonate are preferred.Suitable bicarbonates to be used herein include any alkali metal salt ofbicarbonate like lithium, sodium, potassium and the like, amongst whichsodium and potassium bicarbonate are preferred. However, the choice ofcarbonate or bicarbonate or mixtures thereof may be made depending onthe pH desired in the aqueous medium wherein the granules are dissolved.For example where a relative high pH is desired in the aqueous medium(e.g., above pH 9.5) it may be preferred to use carbonate alone or touse a combination of carbonate and bicarbonate wherein the level ofcarbonate is higher than the level of bicarbonate. The inorganic alkaliand/or earth alkali carbonate salt of the compositions of the inventioncomprises preferably a potassium or more preferably a sodium salt ofcarbonate and/or bicarbonate. Preferably, the carbonate salt comprisessodium carbonate, optionally also a sodium bicarbonate.

The inorganic carbonate salts herein are preferably present at a levelof at least 20% by weight of the composition. Preferably they arepresent at a level of at least 23% or even 25% or even 30% by weight,preferably up to about 60% by weight or more preferably up to 55% oreven 50% by weight.

They may be added completely or partially as separate powdered orgranular component, as cogranules with other detergent ingredients, forexample other salts or surfactants. In solid detergent composiaticns ofthe invention, they may also completely or partially be present indetergent granules such as agglomerates or spray dried granules.

In one embodiment of the invention, an effervescence source is present,preferably comprising an organic acid, such as carboxylic acids oraminoacids, and a carbonate. Then it may be preferred that part or allof the carbonate salt herein is premixed with the organic acid, and thuspresent in an separate granular component.

Preferred effervescent source are selected from compressed particles ofcitric acid and carbonate optionally with a binder; and particle ofcarbonate, bicarbonate and malic or maleic acid in weight ratios of4:2:4. The dry add form of citric acid and carbonate are preferablyused.

The carbonate may have any particle size. In one embodiment, inparticular when the carbonate salt is present in a granule and not asseparately added compound, the carbonate salt has preferably a volumemedian particle size from 5 to 375 microns, whereby preferably at least60%, preferably at least 70% or even at least 80% or even at least 90%by volume, has a particle size of from 1 to 425 microns. Morepreferably, the carbon dioxide source has a volume median particle sizeof 10 to 250, whereby preferably at least 60%, or even at least 70% oreven at least 80% or even at least 90% by volume, has a particle size offrom 1 to 375 microns; or even preferably a volume median particle sizefrom 10 to 200 microns, whereby preferably at least 60%, preferably atleast 70% or even at least 80% or even at least 90% by volume, has aparticle size of from 1 to 250 microns.

In particular when the carbonate salt is added as separate component, soto say ‘dry-added’ or admixed to the other detergent ingredients, thecarbonate may have any particle size, including the above specifiedparticle sizes, but preferably at least an volume average particle sizeof 200 microns or even 250 microns or even 300 microns.

It may be preferred that the carbon dioxide source of the requiredparticle size is obtained by grinding a larger particle size material,optionally followed by selecting the material with the required particlesize by any suitable method.

Whilst percarbonate salts may be present in the compositions of theinvention as a bleaching agent, they are not included in the carbonatesalts as defined herein

Other preferred optional ingredients include enzyme stabilisers,polymeric soil release agents, materials effective for inhibiting thetransfer of dyes from one fabric to another during the cleaning process(i.e., dye transfer inhibiting agents), polymeric dispersing agents,suds suppressors, optical brighteners or other brightening or whiteningagents, anti-static agents, other active ingredients, carriers,hydrotropes, processing aids, dyes or pigments, solvents forliquid-formulations and solid fillers for bar compositions.

Still in another aspect of the invention, there is provided a packagedcomposition comprising the processed product of the invention orcomposition of the invention. Preferably, the packaged composition is aclosed packaging system having a moisture vapour transmission rate ofless than 20 g/m²/24 hours. Typical disclosure of such a package can befound in WO 98/40464.

Still in a further embodiment of the invention, the package is adispensing means. Typical disclosure of such spray dispenser can befound in WO 96/04940 page 19 line 21 to page 22 line 27.

Method of Use

Also provided herein is a method for providing a delayed release of anactive ketone or aldehyde which comprises the step of contacting thesurface to be treated with a a compound or composition of the invention,and thereafter contacting the treated surface with a material,preferably an aqueous medium like moisture or any other meanssusceptible of releasing the perfume from the amine reaction product.

By “surface”, it is meant any surface onto which the compound candeposit. Typical examples of such material are fabrics, hard surfacessuch as dishware, floors, bathrooms, toilet, kitchen and other surfacesin need of a delayed release of a perfume ketone and/or aldehyde such asthat with litter like animal litter. Preferably, the surface is selectedfrom a fabric, a tile, a ceramic; more preferably is a fabric.

By “delayed release” is meant release of the active component (e.g.perfume) over a longer period of time than by the use of the active(e.g., perfume) itself.

Still in another aspect of the invention, there is provided the use ofthe product of the invention for the manufacture of a laundry andcleaning composition for delivering residual fragrance and fabric care,in particular color care, onto the fabrics on which it is applied.

The following are synthesis examples of compounds as defined in thepresent invention:

I-Synthesis of ethyl 4-aminobenzoate with2,4dimethyl-3-cyclohexen-1-carboxaldehyde

To an ice cooled stirred solution of 10 g of2,4-dimethyl-3-cyclohexen-1-carboxaldehyde (0.07 mol) in 35 mL EtOH andmolecular sieves (4A, 20 g) 1 eq of the amine was added via an additionfunnel. The reaction, mixture was stirred under nitrogen atmosphere andprotected from light. After 6 days the mixture was filtrated and thesolvent was removed. The yield of imine formation is about 90%.

Similar results were obtained where the2,4-dimethyl-3-cyclohexen-1-carboxaldehyde was replaced by bourgeonal,trans-2-nonenal, or trans-2-hexenal.

II-Synthesis of 1,4-bis-(3-aminopropyl)-piperazine with α-Damascone

In order to substitute both primary amine groups with a perfume, 2 eq ofperfume were used for 1eq of amino functional polymer. To an ice cooledstirred solution of 1 mmol of α-Damascone in 6 mL EtOH and molecularsieves (4 Å, 20 g), 0.5 eq of 1,4-bis-(3-aminopropyl)-piperazine wasadded via an addition funnel. The reaction mixture was stirred undernitrogen atmosphere and protected from light. After the disappearance ofthe absorption peak from the NMR spectrum of the free perfume rawmaterial (from 3 to 16 hours), the mixture was filtrated and the solventwas removed by vacuum distillation. The yield of β-aminoketone formationis about 90%.

Similar results were obtained where the α-Damascone was replaced by2,4-dimethyl-3-cyclohexen-1-carboxaldehyde, vertocitral, bourgeonal,δ-Damascone or citronellal. In these instances, Schiff-bases are formed.

III-Synthesis of Lupasol with Damascones and2,4-dimethyl-3-cyclohexen-1-carboxaldehyde

The β-amino ketone from Lupasol G100 (commercially available from BASFwith a content of 50% water, 50% Lupasol G100 (Mw. 5000)) and(α-Damascone (or δ-Damascone) was prepared using any one of these threedifferent procedures described as follows:

1. Commercially available Lupasol G100 was dried using the followingprocedure: 20 g of the Lupasol solution was dried at the rotatingevaporator during several hours. The obtained residue, still containingabout 4.5 g of H₂O, was azeotropically distilled at the rotatingevaporator using toluene. The residue was then placed in the desiccatordried at 60° C. (using P205 as water absorbing material). On basis ofthe obtained weight we concluded that the oil contained less then 10%H₂O. On basis of the NMR-spectra we concluded that this is probably lessthen 5%. This dried sample was then used in the preparation of β-aminoketones.

1.38 g of the dried Lupasol G100 obtained above was dissolved in 7 ml.ethanol. The solution was stirred gently with a magnetic stirrer duringa few minutes before 2 g Na₂SO₄ (anhydrous) was added. After stirringagain for a few minutes 2.21 g α-Damascone was added over a period of 1minute. After two days reaction, the mixture was filtrated over a Celitefilter (vide supra), and the residue washed thoroughly with ethanol.About 180 ml. of a light foaming filtrate was obtained. This wasconcentrated until dryness using a rotating evaporator and dried overP₂O₅ in an desiccator at room temperature. About 3.5 of a colorless oilwas obtained.

2. 4.3 g Lupasol G100 solution was without drying dissolved in 10 ml.ethanol. The solution was stirred with a magnetic stirrer during a fewminutes before 3.47 g α-Damascone was added over a 1.5 minutes period.After two days reaction at room temperature the reaction mixture wasfiltrated over Celite (vide supra) and the residue washed thoroughlywith ethanol. The filtrate (200 ml., light foaming) was concentrated atthe evaporator and dried in an desiccator (P₂O₅ as drying agent) at roomtemperature. About 5.9 g of a colorless oil was obtained.

3. To 3.0 g of Lupasol G100 solution (used as such) was added 2.41 gα-Damascone. The mixture was stirred without using solvent. Afterstirring for 4 days the obtained oil was dissolved in 100 ml. THF, driedwith MgSO₄, filtrated and the filtrate concentrated at the rotatingevaporator. After drying in the desiccator (P₂O₅) at room temperatureabout 4 g of a colorless oil was obtained. This oil still containedabout 13% (w/w) of THF, even after a prolonged drying (3 days).

The product obtained from the three procedures had identicalNMR-spectra.

Similar results are obtained where Lupasol G35 or Lupasol HF is usedinstead of Lupasol G100.

Similar results were obtained where the α-Damascone was replaced by2,4-dimethyl-3-cyclohexen-1-carboxaldehyde.

Still another possible route of synthesis is by using Lupasol P. Theβ-amino ketone from Lupasol P and α-Damascone was prepared using theprocedure described as follows:

1.8 g Lupasol P solution (50% H₂O, 50% Lupasol Mw. 750000, as obtainedfrom BASF) was dissolved in 7 ml ethanol, the solution was stirred for afew minutes with a magnetic stirrer before 1.44 g α-Damascone was added.After three days the reaction mixture was filtrated over a celite filter(vide supra) and the residue washed thoroughly with ethanol. Afterconcentrating of the filtrate and drying of the obtained oil in thedesiccator (P₂O₅) at room temperature, about 3 g of the reaction productbetween Lupasol and α-Damascone was obtained.

Processing Method

Processing of the amine reaction product with the carrier is done ashereinbefore described. In particular, 20 g of amine reaction product asabove synthesised is mixed in an Ultra Turrax containing 80 g ofcarrier, e.g. TAE80 for 5 minutes, the temperature of mixing being ofabout 70° C., and the speed of the mixer being sufficient so as tomaintain such temperature substantially constant. Temperature and timewill depend on the nature of the carrier but are a conventional step toskilled man. The resulting mixture is maintained at a temperaturesubstantially equal to the melting point of the carrier material. Oncethe mixture is at a suitable temperature, it is poured onto the coatingmaterial and agglomerated in an electrical mixer like a Braun Mixer.Care is also taken that the temperature during the mixing does notsubstantially exceed the melting point of the carrier material. Forexample, 150 g of a mixture containing TAE80 and 20% of the aminereaction product is poured at 60° C. into a Braun Mixer containing 300 gof carbonate. The mixing of the ingredients is carried out for about 5minutes. Care is also taken that the temperature during the mixing doesnot exceed 65° C. Again, temperature and time will depend on the natureof the coating agent but are conventional step to skilled man.

Abbreviations Used in the Following Laundry and Cleaning CompositionExamples

In the laundry and cleaning compositions, the abbreviated componentidentifications have the following meanings:

DEQA: Di-(tallowyl-oxy-ethyl)dimethyl ammonium chloride

DTDMAC: Ditallow dimethylammonium chloride

DEQA (2): Di-(soft-tallowyloxyethyl)hydroxyethyl methyl ammoniummethylsulfate.

DTDMAMS: Ditallow dimethyl ammonium methylsulfate.

SDASA: 1:2 ratio of stearyldimethyl amine:triple-pressed stearic acid.

Fatty acid: Stearic acid of IV=0

Electrolyte: Calcium chloride

PEG: Polyethylene Glycol 4000

Neodol 45-13: C14-C15 linear primary alcohol ethoxylate, sold by ShellChemical CO.

Silicone antifoam: Polydimethylsiloxane foam controller withsiloxane-oxyalkylene copolymer as dispersing agent with a ratio of saidfoam controller to said dispersing agent of 10:1 to 100:1.

PEI: Polyethyleneimine with an average molecular weight of 1800 and anaverage ethoxylation degree of 7 ethyleneoxy residues per nitrogen

HEDP: 1,1-hydroxyethane diphosphonic acid

LAS: Sodium linear C₁₁₋₁₃ alkyl benzene sulfonate

TAS: Sodium tallow alkyl sulfate

CxyAS: Sodium C_(1x)-C_(1y) alkyl sulfate

C46SAS: Sodium C₁₄-C₁₆ secondary (2,3) alkyl sulfate

CxyEzS: Sodium C_(1x)-C_(1y) alkyl sulfate condensed with z moles ofethylene oxide

CxyEz: C_(1x)-C_(1y) predominantly linear primary alcohol condensed withan average of z moles of ethylene oxide

QAS: R₂.N⁺(CH₃)₂(C₂H₄OH) with R₂=C₁₂-C₁₄

QAS 1: R₂.N⁺(CH₃)₂(C₂H₄OH) with R₂=C₈-C₁₁

APA: C₈-C₁₀ amido propyl dimethyl amine

Soap: Sodium linear alkyl carboxylate derived from an 80/20 mixture oftallow and coconut fatty acids

STS: Sodium toluene sulphonate

CFAA: C₁₂-C₁₄ (coco) alkyl N-methyl glucamide

TFAA: C₁₆-C₁₈ alkyl N-methyl glucamide

TPKFA: C₁₂-C₁₄ topped whole cut fatty acids

STPP: Anhydrous sodium tripolyphosphate

TSPP: Tetrasodium pyrophosphate

Zeolite A: Hydrated sodium aluminosilicate of formula

Na₁₂(AlO₂SiO₂)₁₂.27H₂O

having a primary particle size in the range from 0.1 to 10 micrometers(weight expressed on an anhydrous basis)

NaSKS-6: Crystalline layered silicate of formula δ-Na₂Si₂O₅

Citric acid: Anhydrous citric acid

Borate: Sodium borate

Carbonate: Anydrous sodium carbonate with a particle size between 200 μmand 900 μm

Bicarbonate: Anhydrous sodium bicarbonate with a particle sizedistribution between 400 μm and 1200 μm

Silicate: Amorphous sodium silicate (SiO₂:Na₂O=2.0:1)

Sulfate: Anhydrous sodium sulfate

Mg sulfate: Anhydrous magnesium sulfate

Citrate: Tri-sodium citrate dihydrate of activity 86.4% with a particlesize distribution between 425 μm and 850 μm

MA/AA: Copolymer of 1:4 maleic/acrylic acid, average molecular weightabout 70,000

MA/AA: (1): Copolymer of 4:6 maleic/acrylic acid, average molecularweight about 10,000

AA: Sodium polyacrylate polymer of average molecular weight 4,500

CMC: Sodium carboxymethyl cellulose

Cellulose ether: Methyl cellulose ether with a degree of polymerizationof 650 available from Shin Etsu Chemicals

Protease: Proteolytic enzyme, having 3.3% by weight of active enzyme,sold by NOVO Industries A/S under the tradename Savinase

Protease I: Proteolytic enzyme, having 4% by weight of active enzyme, asdescribed in WO 95/10591, sold by Genencor Int. Inc.

Alcalase: Proteolytic enzyme, having 5.3% by weight of active enzyme,sold by NOVO Industries A/S

Cellulase: Cellulytic enzyme, having 0.23% by weight of active enzyme,sold by NOVO Industries A/S under the tradename Carezyme

Amylase: Amylolytic enzyme, having 1.6% by weight of active enzyme, soldby NOVO Industries A/S under the tradename Termamyl 120T

Lipase: Lipolytic enzyme, having 2.0% by weight of active enzyme, soldby NOVO Industries A/S under the tradename Lipolase

Lipase (1): Lipolytic enzyme, having 2.0% by weight of active enzyme,sold by NOVO Industries A/S under the tradename Lipolase Ultra

Endolase: Endoglucanase enzyme, having 1.5% by weight of active enzyme,sold by NOVO Industries A/S

PB4: Sodium perborate tetrahydrate of nominal formula

NaBO₂.3H₂O.H₂O₂

PB1: Anhydrous sodium perborate bleach of nominal formula

NaBO₂.H₂O₂

Percarbonate: Sodium percarbonate of nominal formula

2Na₂CO₃.3H₂O₂

NOBS: Nonanoyloxybenzene sulfonate in the form of the sodium salt

NAC-OBS: (6-nonamidocaproyl)oxybenzene sulfonate

TAED: Tetraacetylethylenediamine

DTPA: Diethylene triamine pentaacetic acid

DTPMP: Diethylene triamine penta(methylene phosphonate), marketed byMonsanto under, the Tradename Dequest 2060

EDDS: Ethylenediamine-N,N′-disuccinic acid, (S,S) isomer in the form ofits sodium salt.

Photoactivated bleach (1): Sulfonated zinc phthlocyanine encapsulated indextrin soluble polymer

Photoactivated bleach (2): Sulfonated alumino phthlocyanine encapsulatedin dextrin soluble polymer

Brightener 1: Disodium 4,4′-bis(2-sulphostyryl)biphenyl

Brightener 2: Disodium4,4′-bis(4-anilino-6-morpholino-1,3,5-triazin-2-yl)amino)stilbene-2:2′-disulfonate

HEDP: 1,1-hydroxyethane diphosphonic acid

PEGx: Polyethylene glycol, with a molecular weight of x (typically4,000)

PEO: Polyethylene oxide, with an average molecular weight of 50,000

TEPAE: Tetraethylenepentaamine ethoxylate

PVI: Polyvinyl imidosole, with an average molecular weight of 20,000

PVP: Polyvinylpyrolidone polymer, with an average molecular weight of60,000

PVNO: Polyvinylpyridine N-oxide polymer, with an average molecularweight of 50,000

PVPVI: Copolymer of polyvinylpyrolidone and vinylimidazole, with anaverage molecular weight of 20,000

QEA:bis((C₂H₅O)(C₂H₄O)_(n))(CH₃)—N⁺—C₆H₁₂—N⁺—(CH₃)bis((C₂H₅O)—(C₂H₄O))_(n),wherein n=from 20 to 30

SRP 1: Anionically end capped poly esters

SRP 2: Diethoxylated poly (1,2 propylene-terephtalate) short blockpolymer

PEI: Polyethyleneimine with an average molecular weight of 1800 and anaverage ethoxylation degree of 7 ethyleneoxy residues per nitrogen

Silicone antifoam: Polydimethylsiloxane foam controller withsiloxane-oxyalkylene copolymer as dispersing agent with a ratio of saidfoam controller to said dispersing agent of 10:1 to 100:1

Opacifier: Water based monostyrene latex mixture, sold by BASFAktiengesellschaft under the tradename Lytron 621

Wax: Paraffin wax

PA30: Polyacrylic acid of average molecular weight of between about4,500-8,000.

480N: Random copolymer of 7:3 acrylate/methacrylate, average molecularweight about 3,500.

Polygel/carbopol: High molecular weight crosslinked polyacrylates.

Metasilicate: Sodium metasilicate (SiO₂:Na₂O ratio=1.0).

Nonionic: C₁₃-C₁₅ mixed ethoxylated/propoxylated fatty alcohol with anaverage degree of ethoxylation of 3.8 and an average degree ofpropoxylation of 4.5.

Neodol 45-13: C14-C15 linear primary alcohol ethoxylate, sold by ShellChemical CO.

MnTACN: Manganese 1,4,7-trimethyl-1,4,7-triazacyclononane.

PAAC: Pentaamine acetate cobalt(III) salt.

Paraffin: Paraffin oil sold under the tradename Winog 70 by Wintershall.

NaBz: Sodium benzoate.

BzP: Benzoyl Peroxide.

SCS: Sodium cumene sulphonate.

BTA: Benzotriazole.

PH: Measured as a 1% solution in distilled water at 20° C.

PARP1: Processed amine reaction product of ethyl 4-aminobenzoate with2,4-dimethyl-3-cyclohexen-1-carboxaldehyde as made from Synthesisexample 1, mixed with TAE80 carrier and agglomerated with a coatingagent according to processing method above described.

PARP2: Processed amine reaction product of Lupasol G35 with α-Damasconeas made from Synthesis example III, mixed with TAE100 carrier andagglomerated with a coating agent according to processing method abovedescribed.

PARP3: Processed amine reaction product of Lupasol HF with δ-Damasconeas made from Synthesis example III, mixed with TAE80 carrier andagglomerated with a coating agent according to processing method abovedescribed.

PARP4: Processed amine reaction product of BNPP with δ-Damascone as madefrom Synthesis example II, mixed with PEG4000 carrier and agglomeratedwith a coating agent according to processing method above described.

PARP5: Processed amine reaction product of LupasolG100 with2,4-dimethyl-3-cyclohexen-1-carboxaldehyde as made from Synthesisexample III, mixed with a TAE80 carrier and agglomerated with a coatingagent according to processing method above described.

PARP6: Processed amine reaction product of ethyl 4-aminobenzoate withtrans-2-nonenal as made from Synthesis example II, mixed with a TAE80carrier and agglomerated with a coating agent according to processingmethod above described.

PARP7: Processed amine reaction product of ethyl 4-aminobenzoate withtrans-2-hexenal as made from Synthesis example I, mixed with TAE80carrier and agglomerated with a coating agent according to processingmethod above described.

Clay I: Bentonite clay

Clay II: Smectite clay

Flocculating agent I: polyethylene oxide of average molecular weight ofbetween 200,000 and 400,000

Flocculating agent II: polyethylene oxide of average molecular weight ofbetween 400,000 and 1,000,000

Flocculating agent III: polymer of acrylamide and/or acrylic acid ofaverage molecular weight of 200,000 and 400,000

DOBS: Decanoyl oxybenzene sulfonate in the form of the sodium salt

SRP 3: Polysaccharide soil release polymer

SRP 4: Nonionically end capped poly esters

Polymer: Polyvinylpyrrolidone K90 available from BASF under thetradename Luviskol K90

Dye fixative: Dye fixative commercially available from Clariant underthe tradename Cartafix CB

Polyamine: 1,4-Bis-(3-aminopropyl)piperazine

Bayhibit AM: 2-Phosphonobutane-1,2,4-tricarboxylic acid commerciallyavailable from Bayer

Fabric softener active: Di-(canoloyl-oxy-ethyl)hydroxyethyl methylammonium methylsulfate

HPBDC: Hydroxypropyl beta-cyclodextrin

RAMEB: Randomly methylated beta-cyclodextrin

Bardac 2050: Dioctyl dimethyl ammonium chloride, 50% solution

Bardac 22250: Didecyl dimethyl ammonium chloride, 50% solution

Genamin C100: Coco fatty amine ethoxylated with 10 moles ethylene oxideand commercially available from Clariant

Genapol V4463: Coco alcohol ethoxylated with 10 moles ethylene oxide andcommercially available from Clariant

Silwet 7604: Polyalkyleneoxide polysiloxanes of MW 4000 of formula

R—(CH₃)₂SiO—[(CH₃)₂SiO]_(a)—[(CH₃)(R)SiO]_(b)—Si(CH₃)₂—R,

wherein average a+b is 21, and commercially available from OsiSpecialties, Inc., Danbury, Conn.

Silwet 7600: Polyalkyleneoxide polysiloxanes of MW 4000, of formula

R—(CH₃)₂SiO—[(CH₃)₂SiO]_(a)—[(CH₃)(R)SiO]_(b)—Si(CH₃)₂—R,

wherein average a+b is 11, and commercially available from OsiSpecialties, Inc., Danbury, Conn.

In the following formulation examples all levels are quoted as % byweight of the composition unless otherwise stated, and incorporation ofthe processed amine reaction product so called herein after “PARP” inthe fully formulated composition is carried out by dry addition (d) inthe composition as defined herein before. The term in bracket for thePARP in the formulation examples refers to the type of coating (c) forcarbonate coating and (s) for starch coating.

EXAMPLE 1

The following high density granular laundry detergent compositions A toG were prepared in accord with the invention:

A0 A1 A B C D E F G LAS 6.0 6.0 8.0 8.0 8.0 2.0 6.0 6.0 5.0 TAS 1.0 0.1— 0.5 — 0.5 1.0 0.1 1.5 C46(S)AS — — 2.0 2.5 — — — — — C25AS 4.5 5.5 — —— 7.0 4.5 5.5 2.5 C68AS — — 2.0 5.0 7.0 — — — 0.2 C25E5 4.6 4.6 — — 3.410.0 4.6 4.6 2.6 C25E7 — — 3.4 3.4 1.0 — — — — C25E3S 5.0 4.5 — — — 2.05.0 4.5 0.5 QAS — — — 0.8 — — — — — QAS (I) 0.5 1.0 — — — 0.8 0.5 1.01.5 Zeolite A 20.0 18.1 18.1 18.0 14.1 18.1 20.0 18.1 16.2 Citric acid —2.5 — — — 2.5 — 2.5 1.5 Carbonate 10.0 13.0 13.0 13.0 25.0 10.0 10.013.0 20.6 SKS-6 — 10.0 — — — 10.0 — 10.0 4.3 Silicate 0.5 0.3 1.4 1.43.0 0.3 0.5 0.3 — Citrate — — — 1.0 — 3.0 — — 1.4 Sulfate — — 26.1 26.126.1 6.0 — — Mg sulfate — 0.2 0.3 — — 0.2 — 0.2 0.03 MA/AA 1.0 1.0 0.30.3 0.3 4.0 1.0 1.0 0.6 CMC 0.4 0.4 0.2 0.2 0.2 0.2 0.4 0.4 0.3 PB4 — —9.0 9.0 5.0 — — — — Percarbonate 18.0 18.0 — — — — 18.0 18.0 9.0 TAED3.9 4.2 1.5 0.4 1.5 — 3.9 4.2 3.2 NAC-OBS — — — 2.0 1.0 — — — DTPMP — —0.25 0.25 0.25 0.25 — — — SRP 2 — 0.2 — — — 0.2 — 0.2 — EDDS 0.5 0.5 —0.25 0.4 — 0.5 0.5 0.1 TFAA — — — 1.0 — 2.0 — — 1.1 CFAA — — — 1.0 — 2.0— — — HEDP 0.4 0.4 0.3 0.3 0.3 0.3 0.4 0.4 0.3 QEA — 0.5 — — — 0.2 — 0.5— Protease I — — — — 0.26 1.0 — — 0.3 Protease 1.5 1.0 0.26 0.26 — — 1.51.0 — Cellulase 0.3 0.3 0.3 — — 0.3 0.3 0.3 0.3 Amylase 0.5 0.5 0.1 0.10.1 0.4 0.5 0.5 0.1 Lipase (1) 0.5 0.5 0.3 — — 0.5 0.5 0.5 0.1Photoactivated 20 20 15 15 15 — 20 20 20 bleach ppm ppm ppm ppm ppm ppmppm ppm (ppm) PVNO/PVP — — — — — 0.1 — — — VI Brightener 1 0.09 0.090.09 0.09 0.09 — 0.09 0.09 0.01 Brightener 2 — — — — — — — — 0.09Perfume 0.4 0.4 0.3 0.3 0.3 0.4 0.4 0.4 0.4 spray on PARP 3 — — 10 5 — —5 1 4 (c) (s) (c) (c) (c) PARP 5 — — — — 2 8 4 — — (c) (c) (s) PARP 6 51 — — — — — — — (c) (c) PARP 7 4 — — — — — — — — (s) Silicone 0.3 0.30.5 0.5 0.5 — 0.3 0.3 0.3 antifoam Clay II — — — — — — — — 12.0Flocculating — — — — — — — — 0.3 agent I Glycerol — — — — — — — — 0.6Wax — — — — — — — — 0.4 Misc/minors to 100% Density in 850 850 850 850850 850 850 850 850 g/liter

EXAMPLE 2

The following franular laundry detergent compositions of particularutility under European machine wash conditions were prepared in accordwith the invention.

A B C D E F LAS 5.5 7.5 5.0 5.0 6.0 7.0 TAS 1.25 1.86 — 0.8 0.4 0.3C24AS/C25AS — 2.24 5.0 5.0 5.0 2.2 C25E3S — 0.76 1.0 1.5 3.0 1.0 C45E73.25 — — — — 3.0 TFAA — — 2.0 — — — C25E5 — 5.5 — — — — QAS 0.8 — — — —— QAS II — 0.7 1.0 0.5 1.0 0.7 STPP 19.7 — — — — — Zeolite A — 19.5 25.019.5 20.0 17.0 NaSKS-6/citric acid — 10.6 — 10.6 — — (79:21) NaSKS-6 — —9.0 — 10.0 10.0 Carbonate 6.1 10.0 9.0 10.0 10.0 18.0 Bicarbonate — 2.07.0 5.0 — 2.0 Silicate 6.8 — — 0.3 0.5 — Citrate — — 4.0 4.0 — — Sulfate39.8 — — 5.0 — 12.0 Mg sulfate — — 0.1 0.2 0.2 — MA/AA 0.5 1.6 3.0 4.01.0 1.0 CMC 0.2 0.4 1.0 1.0 0.4 0.4 PB4 5.0 12.7 — — — — Percarbonate —— — — 18.0 15.0 TAED 0.5 3.1 — — 5.0 — NAC-OBS 1.0 3.5 — — — 2.5 DTPMP0.25 0.2 0.3 0.4 — 0.2 HEDP — 0.3 — 0.3 0.3 0.3 QEA — — 1.0 1.0 1.0 —Protease I — — — 0.5 1.2 — Protease 0.26 0.85 0.9 1.0 — 0.7 Lipase (1)0.15 0.15 0.3 0.3 0.3 0.2 Cellulase 0.28 0.28 0.2 0.2 0.3 0.3 Amylase0.1 0.1 0.4 0.4 0.6 0.2 PVNO/PVPVI — — 0.2 0.2 — — PVP 0.9 1.3 — — — 0.9SRP 1 — — 0.2 0.2 0.2 — Photoactivated 15 27 — — 20 20 bleach (1) (ppm)ppm ppm ppm ppm Photoactivated 15 — — — — — bleach (2) (ppm) ppmBrightener 1 0.08 0.19 — — 0.09 0.15 Brightener 2 — 0.04 — — — — Perfume0.3 0.3 0.4 0.3 0.4 0.3 PARP1 1.0 10.0 5.0 — — — (c) (c) (c) PARP2 — —2.0 4.0 8.0 2.0 (c) (s) (c) (c) Silicone antifoam 0.5 2.4 0.3 0.5 0.32.0 Minors/misc to 100% Density in g/liter 750 750 750 750 750 750

EXAMPLE 3

The following detergent formulations of particular utility underEuropean machine wash conditions were prepared in accord with theinvention.

A B C D Blown powder LAS 6.0 5.0 11.0 6.0 TAS 2.0 — — 2.0 Zeolite A 24.0— — 20.0 STPP — 27.0 24.0 — Sulfate 4.0 6.0 13.0 — MA/AA 1.0 4.0 6.0 2.0Silicate 1.0 7.0 3.0 3.0 CMC 1.0 1.0 0.5 0.6 Brightener 1 0.2 0.2 0.20.2 Silicone antifoam 1.0 1.0 1.0 0.3 DTPMP 0.4 0.4 0.2 0.4 Spray onBrightener 0.02 — — 0.02 C45E7 — — — 5.0 C45E2 2.5 2.5 2.0 — C45E3 2.62.5 2.0 — Perfume 0.5 0.3 0.5 0.2 Silicone antifoam 0.3 0.3 0.3 — Dryadditives QEA — — — 1.0 EDDS 0.3 — — — Sulfate 2.0 3.0 5.0 10.0Carbonate 6.0 13.0 11.0 14.0 Citric acid 2.5 — — 2.0 QAS II 0.5 — — 0.5SKS-6 10.0 — — — Percarbonate 18.5 — — — PB4 — 18.0 10.0 21.5 TAED 2.02.0 — 2.0 NAC-OBS 3.0 2.0 4.0 — Protease 1.0 1.0 1.0 1.0 Lipase — 0.4 —0.2 Lipase(1) 0.4 — 0.4 — Amylase 0.2 0.2 0.2 0.4 Brightener 1 0.05 — —0.05 PARP3 2.0(c) 1.0(c) 4.0(s) 2.0(c) Misc/minor to 100%

EXAMPLE 4

The following granular detergent formulations were prepared in accordwith the invention.

A B C D E F Blown powder LAS 23.0 8.0 7.0 9.0 7.0 7.0 TAS — — — — 1.0 —C45AS 6.0 6.0 5.0 8.0 — — C45AES — 1.0 1.0 1.0 — — C45E35 — — — — 2.04.0 Zeolite A 10.0 18.0 14.0 12.0 10.0 10.0 MA/AA — 0.5 — — — 2.0 MA/AA(1) 7.0 — — — — — AA — 3.0 3.0 2.0 3.0 3.0 Sulfate 5.0 6.3 14.3 11.015.0 19.3 Silicate 10.0 1.0 1.0 1.0 1.0 1.0 Carbonate 13.0 19.0 8.0 20.78.0 6.0 PEG 4000 0.4 1.5 1.5 1.0 1.0 1.0 DTPA — 0.9 0.5 — — 0.5Brightener 2 0.3 0.2 0.3 — 0.1 0.3 Spray on C45E7 — 2.0 — — 2.0 2.0C25E9 3.0 — — — — — C23E9 — — 1.5 2.0 — 2.0 Perfume 0.3 0.3 0.3 2.0 0.30.3 Agglomerates C45AS — 5.0 5.0 2.0 — 5.0 LAS — 2.0 2.0 — — 2.0 ZeoliteA — 7.5 7.5 8.0 — 7.5 Carbonate — 4.0 4.0 5.0 — 4.0 PEG 4000 — 0.5 0.5 —— 0.5 Misc (water etc) — 2.0 2.0 2.0 — 2.0 Dry additives QAS (I) — — — —1.0 — Citric acid — — — — 2.0 — PB4 — — — — 12.0 1.0 PB1 4.0 1.0 3.0 2.0— — Percarbonate — — — — 2.0 10.0 Carbonate — 5.3 1.8 — 4.0 4.0 NOBS 4.0— 6.0 — — 0.6 Methyl cellulose 0.2 — — — — — SKS-6 8.0 — — — — — STS — —2.0 — 1.0 — Cumene sulfonic acid — 1.0 — — — 2.0 Lipase 0.2 — 0.2 — 0.20.4 Cellulase 0.2 0.2 0.2 0.3 0.2 0.2 Amylase 0.2 — 0.1 — 0.2 — Protease0.5 0.5 0.5 0.3 0.5 0.5 PVPVI — — — — 0.5 0.1 PVP — — — — 0.5 — PVNO — —0.5 0.3 — — QEA — — — — 1.0 — SRP1 0.2 0.5 0.3 — 0.2 — PARP3 2.0(c)1.0(c) 4.0(c) 0.5(c) 3.5(c) 1.0(s) Silicone antifoam 0.2 0.4 0.2 0.4 0.1— Mg sulfate — — 0.2 — 0.2 — Misc/minors to 100% G H I J Blown powderClay I or II 7.0 10.0 6.0 2.0 LAS 16.0 5.0 11.0 6.0 TAS — 5.0 — 2.0Zeolite A — 20.0 — 10.0 STPP 24.0 — 14.0 — Sulfate — 2.0 — — MA/AA — 2.01.0 1.0 Silicate 4.0 7.0 3.0 — CMC 1.0 — 0.5 0.6 Brightener 1 0.2 0.20.2 0.2 Carbonate 10.0 10.0 20.0 — DTPMP 0.4 0.4 0.2 — Spray onBrightener 1 0.02 — — 0.02 C45E7 or E9 — — 2.0 1.0 C45E3 or E4 — — 2.04.0 Perfume 0.5 — 0.5 0.2 Silicone antifoam 0.3 — — — Dry additivesFlocculating agent I or II 0.3 1.0 1.0 0.5 QEA — — — 1.0 HEDP/EDDS 0.3 —— — Sulfate 2.0 — — — Carbonate 20.0 13.0 15.0 24.0 Citric acid 2.5 — —2.0 QAS — — 0.5 0.5 NaSKS-6 3.5 — — 5.0 Percarbonate — — — 9.0 PB4 — —5.0 NOBS — — — 1.3 TAED — — 2.0 1.5 Protease 1.0 1.0 1.0 1.0 Lipase —0.4 — 0.2 Amylase 0.2 0.2 0.2 0.4 Brightener 2 0.05 — — 0.05 Perfume 1.00.2 0.5 0.3 Speckle 1.2 0.5 2.0 — PARP 3 1.0(s) 1.5(c) 3.0(c) 0.8(s)PARP 1 3.0(c) 3.0(s) 2.0(c) 1.0(c) Misc/minor to 100%

EXAMPLE 5

The following nil bleach-containing detergent formulations of particularuse in the washing of coloured clothing, according to the presentinvention were prepared:

A B C Blown Powder Zeolite A 15.0 15.0 — Sulfate 0.0 5.0 — LAS 3.0 3.0 —DTPMP 0.4 0.5 — CMC 0.4 0.4 — MA/AA 4.0 4.0 — Agglomerates C45AS — —11.0 LAS 6.0 5.0 — TAS 3.0 2.0 — Silicate 4.0 4.0 — Zeolite A 10.0 15.013.0 CMC — — 0.5 MA/AA — — 2.0 Carbonate 9.0 7.0 7.0 Spray On Perfume0.3 0.3 0.5 C45E7 4.0 4.0 4.0 C25E3 2.0 2.0 2.0 Dry additives MA/AA — —3.0 NaSKS-6 — — 12.0 Citrate 10.0 — 8.0 Bicarbonate 7.0 3.0 5.0Carbonate 6.0 — 7.0 PVPVI/PVNO 0.5 0.5 0.5 Alcalase 0.5 0.3 0.9 Lipase0.4 0.4 0.4 Amylase 0.6 0.6 0.6 Cellulase 0.6 0.6 0.6 PARP1 7.0(c) 10(c)5.0(c) Silicone antifoam 5.0 5.0 5.0 Dry additives Sulfate 0.0 9.0 0.0Misc/minors to 100% 100.0 100.0 100.0 Density (g/liter) 700 700 700

EXAMPLE 6

The following granular detergent formulations were prepared in accordwith the invention.

A B C D Base granule Zeolite A 30.0 22.0 24.0 10.0 Sulfate 10.0 5.0 10.07.0 MA/AA 3.0 — — — AA — 1.6 2.0 — MA/AA (1) — 12.0 — 6.0 LAS 14.0 10.09.0 20.0 C45AS 8.0 7.0 9.0 7.0 C45AES — 1.0 1.0 — Silicate — 1.0 0.510.0 Soap — 2.0 — — Brightener 1 0.2 0.2 0.2 0.2 Carbonate 6.0 9.0 10.010.0 PEG 4000 — 1.0 1.5 — DTPA — 0.4 — — Spray on C25E9 — — — 5.0 C45E71.0 1.0 — — C23E9 — 1.0 2.5 — Perfume 0.2 0.3 0.3 — Dry additivesCarbonate 5.0 5.0 15.0 6.0 PVPVI/PVNO 0.5 — 0.3 — Protease 1.0 1.0 1.00.5 Lipase 0.4 — — 0.4 Amylase 0.1 — — 0.1 Cellulase 0.1 0.2 0.2 0.1NOBS — 4.0 — 4.5 PB1 1.0 5.0 1.5 6.0 Sulfate 4.0 5.0 — 5.0 SRPI — 0.4 —— PARP1 10(c) 5.0(c) 8.0(c) — PARP3 — 1.0(s) — 2.0(s) Sud supressor —0.5 0.5 — Misc/minor to 100%

EXAMPLE 7

The following granular detergent compositions were prepared in accordwith the invention.

A B C Blown powder Zeolite A 20.0 — 15.0 STPP — 20.0 — Sulphate — — 5.0Carbonate — — 5.0 TAS — — 1.0 LAS 6.0 6.0 6.0 C68AS 2.0 2.0 — Silicate3.0 8.0 — MA/AA 4.0 2.0 2.0 CMC 0.6 0.6 0.2 Brightener 1 0.2 0.2 0.1DTPMP 0.4 0.4 0.1 STS — — 1.0 Spray on C45E7 5.0 5.0 4.0 Siliconeantifoam 0.3 0.3 0.1 Perfume 0.2 0.2 0.3 Dry additives QEA — — 1.0Carbonate 14.0 9.0 10.0 PB1 1.5 2.0 — PB4 18.5 13.0 13.0 TAED 2.0 2.02.0 QAS (I) — — 1.0 Photoactivated bleach 15 ppm 15 ppm 15 ppm SKS-6 — —3.0 Protease 1.0 1.0 0.2 Lipase 0.2 0.2 0.2 Amylase 0.4 0.4 0.2Cellulase 0.1 0.1 0.2 Sulfate 10.0 20.0 5.0 PARP3 5.0(c) 2.0(c) 4.0(s)Misc/minors to 100% Density (g/liter) 700 700 700

EXAMPLE 8

The following detergent compositions, according to the present inventionwere prepared:

A B C Blown Powder Zeolite A 15.0 15.0 15.0 Sulfate 0.0 5.0 0.0 LAS 3.03.0 3.0 QAS — 1.5 1.5 DTPMP 0.4 0.2 0.4 EDDS — 0.4 0.2 CMC 0.4 0.4 0.4MA/AA 4.0 2.0 2.0 Agglomerates LAS 5.0 5.0 5.0 TAS 2.0 2.0 1.0 Silicate3.0 3.0 4.0 Zeolite A 8.0 8.0 8.0 Carbonate 8.0 8.0 4.0 Spray On Perfume0.3 0.3 0.3 C45E7 2.0 2.0 2.0 C25E3 2.0 — — Dry additives Citrate 5.0 —2.0 Bicarbonate — 3.0 — Carbonate 8.0 15.0 10.0 TAED 6.0 2.0 5.0 PB114.0 7.0 10.0 PEO — — 0.2 PARP3 2.0(c) 1.0(c) 0.75(c) Bentonite clay — —10.0 Protease 1.0 1.0 1.0 Lipase 0.4 0.4 0.4 Amylase 0.6 0.6 0.6Cellulase 0.6 0.6 0.6 Silicone antifoam 5.0 5.0 5.0 Dry additives Sodiumsulfate 0.0 3.0 0.0 Misc/minors to 100% 100.0 100.0 100.0 Density(g/liter) 850 850 850 A B C D E Blown Powder STPP/Zeolite A 9.0 15.015.0 9.0 9.0 Flocculating agent II 0.5 0.2 0.9 1.5 — or III LAS 7.5 23.03.0 7.5 7.5 QAS 2.5 1.5 — — — DTPMP 0.4 0.2 0.4 0.4 0.4 HEDP or EDDS —0.4 0.2 — — CMC 0.1 0.4 0.4 0.1 0.1 Sodium carbonate 5.0 20.0 20.0 10.0— Brightener 0.05 — — 0.05 0.05 Clay I or II — 10.0 — — — STS 0.5 — —0.5 0.5 MA/AA 1.5 2.0 2.0 1.5 1.5 Agglomerates Suds suppresser 1.0 1.0 —2.0 0.5 (silicon) Agglomerate Clay 9.0 — — 4.0 10.0 Wax 0.5 — — 0.5 1.5Glycerol 0.5 — — 0.5 0.5 Agglomerate LAS — 5.0 5.0 — — TAS — 2.0 1.0 — —Silicate — 3.0 4.0 — — Zeolite A — 8.0 8.0 — — Carbonate — 8.0 4.0 — —Spray On Perfume 0.3 — — 0.3 0.3 C45E7 or E9 2.0 — — 2.0 2.0 C25E3 or E42.0 — — 2.0 2.0 Dry additives Citrate or citric acid 2.5 — 2.0 2.5 2.5Clay I or II — 5.0 5.0 — — Flocculating agent I — — — — 0.2 or IIBicarbonate — 3.0 — — — Carbonate 15.0 — — 25.0 31.0 TAED 1.0 2.0 5.01.0 — Sodium perborate 6.0 7.0 10.0 6.0 — or percarbonate SRP1, 2, 3 or4 0.2 0.1 0.2 0.5 0.3 CMC or nonionic 1.0 1.5 0.5 — — cellulose etherProtease 0.3 1.0 1.0 0.3 0.3 Lipase — 0.4 0.4 — — Amylase 0.2 0.6 0.60.2 0.2 Cellulase 0.2 0.6 0.6 0.2 0.2 Silicone antifoam — 5.0 5.0 — —Perfume (starch) 0.2 0.3 1.0 0.2 0.2 Speckle 0.5 0.5 0.1 — 1.0 NaSKS-6(silicate 3.5 — — — 3.5 2R) Photobleach 0.1 — — 0.1 0.1 Soap 0.5 2.5 —0.5 0.5 Sodium sulfate — 3.0 — — — PARP3 1.5(c) 1.0(c) 0.75(s) 3.0(s)1.0(c) Misc/minors to 100.0 100.0 100.0 100.0 100.0 100% Density(g/liter) 850 850 850 850 850

EXAMPLE 9

The following detergent formulations, according to the present inventionwere prepared:

A B C D LAS 18.0 14.0 24.0 20.0 QAS 0.7 1.0 — 0.7 TFAA — 1.0 — —C23E56.5 — — 1.0 — C45E7 — 1.0 — — C45E3S 1.0 2.5 1.0 — STPP 32.0 18.030.0 22.0 Silicate 9.0 5.0 9.0 8.0 Carbonate 9.0 7.5 — 5.0 Bicarbonate —7.5 — — PB1 3.0 1.0 — — PB4 — 1.0 — — NOBS 2.0 1.0 — — DTPMP — 1.0 — —DTPA 0.5 — 0.2 0.3 SRP 1 0.3 0.2 — 0.1 MA/AA 1.0 1.5 2.0 0.5 CMC 0.8 0.40.4 0.2 PEI — — 0.4 — Sodium sulfate 20.0 10.0 20.0 30.0 Mg sulfate 0.2— 0.4 0.9 Protease 0.8 1.0 0.5 0.5 Amylase 0.5 0.4 — 0.25 Lipase 0.2 —0.1 — Cellulase 0.15 — — 0.05 Photoactivated 30 ppm 20 ppm — 10 ppmbleach (ppm) PARP4 2.0(c) 4.0(s) 8.0(c) 0.8(c) Perfume spray 0.3 0.3 0.10.2 on Brightener 1/2 0.05 0.2 0.08 0.1 Misc/minors to 100%

EXAMPLE 10

The following liquid detergent formulations were prepared in accord withthe invention (levels are given as parts per weight).

A B C D E LAS 11.5 8.8 — 3.9 — C25E2.5S — 3.0 18.0 — 16.0 C45E2.25S 11.53.0 — 15.7 — C23E9 — 2.7 1.8 2.0 1.0 C23E7 3.2 — — — — CFAA — — 5.2 —3.1 TPKFA 1.6 — 2.0 0.5 2.0 Citric acid (50%) 6.5 1.2 2.5 4.4 2.5Calcium formate 0.1 0.06 0.1 — — Sodium formate 0.5 0.06 0.1 0.05 0.05Sodium cumene sulfonate 4.0 1.0 3.0 1.18 — Borate 0.6 — 3.0 2.0 2.9Sodium hydroxide 5.8 2.0 3.5 3.7 2.7 Ethanol 1.75 1.0 3.6 4.2 2.9 1,2propanediol 3.3 2.0 8.0 7.9 5.3 Monoethanolamine 3.0 1.5 1.3 2.5 0.8TEPAE 1.6 — 1.3 1.2 1.2 Protease 1.0 0.3 1.0 0.5 0.7 Lipase — — 0.1 — —Cellulase — — 0.1 0.2 0.05 Amylase — — — 0.1 — SRP1 0.2 — 0.1 — — DTPA —— 0.3 — — PVNO — — 0.3 — 0.2 PARP1 8.0(c) — — — — PARP2 — 2.0(c) — — —PARP3 — — 1.0(c) — — PARP4 — — — 4.0(s) — PARP5 — — — — 10.0(s)Brightener 1 0.2 0.07 0.1 — — Silicone antifoam 0.04 0.02 0.1 0.1 0.1Water/minors up to 100%

EXAMPLE 11

The following liquid detergent formulations were prepared in accord withthe invention (levels are given in parts per weight):

A B C D E F G H LAS 10.0 13.0 9.0 — 25.0 — — — C25AS 4.0 1.0 2.0 10.0 —13.0 18.0 15.0 C25E3S 1.0 — — 3.0 — 2.0 2.0 4.0 C25E7 6.0 8.0 13.0 2.5 —— 4.0 4.0 TFAA — — — 4.5 — 6.0 8.0 8.0 APA — 1.4 — — 3.0 1.0 2.0 — TPKFA2.0 — 13.0 7.0 — 15.0 11.0 11.0 Citric acid 2.0 3.0 1.0 1.5 1.0 1.0 1.01.0 Dodecenyl/ 12.0 10.0 — — 15.0 — — — tetradecenyl succinic acid Rapeseed fatty 4.0 2.0 1.0 — 1.0 — 3.5 — acid Ethanol 4.0 4.0 7.0 2.0 7.02.0 3.0 2.0 1,2 Propanediol 4.0 4.0 2.0 7.0 6.0 8.0 10.0 13.0 Mono- — —— 5.0 — — 9.0 9.0 ethanolamine Triethanol- — — 8.0 — — — — — amine TEPAE0.5 — 0.5 0.2 — — 0.4 0.3 DTPMP 1.0 1.0 0.5 1.0 2.0 1.2 1.0 — Protease0.5 0.5 0.4 0.25 — 0.5 0.3 0.6 Alcalase — — — — 1.5 — — — Lipase — 0.10— 0.01 — — 0.15 0.15 Amylase 0.25 0.25 0.6 0.5 0.25 0.9 0.6 0.6Cellulase — — — 0.05 — — 0.15 0.15 Endolase — — — 0.10 — — 0.07 — SRP20.3 — 0.3 0.1 — — 0.2 0.1 Boric acid 0.1 0.2 1.0 2.0 1.0 1.5 2.5 2.5Calcium — 0.02 — 0.01 — — — — chloride Bentonite clay — — — — 4.0 4.0 —— Brightener 1 — 0.4 — — 0.1 0.2 0.3 — Sud supressor 0.1 0.3 — 0.1 0.4 —— — Opacifier 0.5 0.4 — 0.3 0.8 0.7 — — PARP1 8 — 5 — 3 — 4 2 (s) (c)(c) (s) (s) PARP3 — 2 — 1 — 8 1 0.7 (c) (c) (c) (c) (c) Water/minors upto 100% NaOH up to 8.0 8.0 7.6 7.7 8.0 7.5 8.0 8.2 pH

EXAMPLE 12

The following liquid detergent compositions were prepared in accord withthe invention (levels are given in parts per weight).

A B LAS 27.6 18.9 C45AS 13.8 5.9 C13E8 3.0 3.1 Oleic acid 3.4 2.5 Citricacid 5.4 5.4 Sodium hydroxide 0.4 3.6 Calcium formate 0.2 0.1 Sodiumformate — 0.5 Ethanol 7.0 — Monoethanolamine 16.5 8.0 1,2 propanediol5.9 5.5 Xylene sulfonic acid — 2.4 TEPAE 1.5 0.8 Protease 1.5 0.6 PEG —0.7 Brightener 2 0.4 0.1 Perfume spray on 0.5 0.3 PARP2 2.0(c) — PARP42.0(c) 1.0(c) Water/minors up to 100%

EXAMPLE 13

The following is a composition in the form of a tablet, bar, extrudateor granule in accord with the invention:

A B C D E F G Sodium C₁₁-C₁₃ 12.0 16.0 23.0 19.0 18.0 20.0 16.0alkylbenzenesulfonate Sodium C₁₄-C₁₅ 4.5 — — — 4.0 alcohol sulfateC₁₄-C₁₅ alcohol — — 2.0 — 1.0 1.0 1.0 ethoxylate (3) sulfate SodiumC₁₄-C₁₅ 2.0 2.0 — 1.3 — — 5.0 alcohol ethoxylate C₉-C₁₄ alkyl dimethyl —— 1.0 0.5 2.0 hydroxy ethyl quaternary ammonium salt Tallow fatty acid —— — — 1.0 Sodium tripoly- 23.0 25.0 14.0 22.0 20.0 10.0 20.0phosphate/Zeolite Sodium carbonate 25.0 22.0 35.0 20.0 28.0 41.0 30.0Sodium Polyacrylate 0.5 0.5 0.5 0.5 — — — (45%) Sodium — — 1.0 1.0 1.02.0 0.5 polyacrylate/maleate polymer Sodium silicate (1:6 3.0 6.0 9.08.0 9.0 6.0 8.0 ratio NaO/SiO₂) (46%) Sodium sulfate — — — — — 2.0 3.0Sodium perborate/ 5.0 5.0 10.0 — 3.0 1.0 — percarbonatePoly(ethyleneglycol), 1.5 1.5 1.0 1.0 — — 0.5 MW ˜4000 (50%) Sodiumcarboxy 1.0 1.0 1.0 — 0.5 0.5 0.5 methyl cellulose NOBS/DOBS — 1.0 — —1.0 0.7 — TAED 1.5 1.0 2.5 — 3.0 0.7 — SRP1 1.5 1.5 1.0 1.0 — 1.0 — ClayI or II 5.0 6.0 12.0 7.0 10.0 4.0 3.0 Flocculating agent I or 0.2 0.23.0 2.0 0.1 1.0 0.5 III Humectant 0.5 1.0 0.5 1.0 0.5 0.5 — Wax 0.5 0.51.0 — — 0.5 0.5 Moisture 7.5 7.5 6.0 7.0 5.0 3.0 5.0 Magnesium sulphate— — — — — 0.5 1.5 Chelant — — — — 0.8 0.6 1.0 Enzymes, including — — — —2.0 1.5 2.0 amylase, cellulase, protease and lipase Speckle 2.5 4.1 4.24.4 5.6 5.0 5.2 minors, e.g. perfume, 2.0 1.0 1.0 1.0 2.5 1.5 1.0 PVP,PVPVI/PVNO, brightener, photo-bleach, PARP5(c) 3.0 3.0 — — — — —PARP3(c) 0.08 0.1 0.2 0.1 0.05 0.08 0.05 aggl 1.0 1.5 3.0 1.5 0.75 1.00.75 salt 0.16 0.2 0.4 0.2 0.1 0.16 0.1 H I J K Sodium C₁₁-C₁₃ 23.0 13.020.0 18.0 alkylbenzenesulfonate Sodium C₁₄-C₁₅ alcohol sulfate — 4.0 — —Clay I or II 5.0 10.0 14.0 6.0 Flocculating agent I or II 0.2 0.3 0.10.9 Wax 0.5 0.5 1.0 — Humectant (glycerol/silica) 0.5 2.0 1.5 — C₁₄-C₁₅alcohol ethoxylate sulfate — — 2.0 Sodium C₁₄-C₁₅ alcohol ethoxylate (2.5 3.5 — — C₉-C₁₄ alkyl dimethyl hydroxy ethyl — — 0.5 quaternaryammonium salt Tallow fatty acid 0.5 — — — Tallow alcohol ethoxylate (50)— — 1.3 Sodium tripolyphosphate — 41.0 — 20.0 Zeolite A, hydrate (0.1-10micron size) 26.3 — 21.3 — Sodium carbonate 24.0 22.0 35.0 27.0 SodiumPolyacrylate (45%) 2.4 — 2.7 — Sodium polyacrylate/maleate polymer — —1.0 2.5 Sodium silicate (1.6 or 2 or 2.2 ratio 4.0 7.0 2.0 6.0 NaO/SiO₂)(46%) Sodium sulfate — 6.0 2.0 — Sodium perborate/percarbonate 8.0 4.0 —12.0 Poly(ethyleneglycol), MW ˜4000 (50%) 1.7 0.4 1.0 — Sodium carboxymethyl cellulose 1.0 — — 0.3 Citric acid — — 3.0 — NOBS/DOBS 1.2 — — 1.0TAED 0.6 1.5 — 3.0 Perfume 0.5 1.0 0.3 0.4 SRP 1 — 1.5 1.0 1.0 Moisture7.5 3.1 6.1 7.3 Magnesium sulphate — — — 1.0 Chelant — — — 0.5 speckle1.0 0.5 0.2 2.7 Enzymes, including amylase, cellulase, — 1.0 — 1.5protease and lipase minors, e.g. brightener, photo-bleach 1.0 1.0 1.01.0 PARP3(c) 1.5 3.0 1.0 4.5

EXAMPLE 14

The following laundry bar detergent compositions were prepared in accordwith the invention (levels are given in parts per weight).

A B C D E F G H LAS — — 19.0 15.0 21.0 6.75 8.8 — C28AS 30.0 13.5 — — —15.75 11.2 22.5 Sodium laurate 2.5 9.0 — — — — — — Zeolite A 2.0 1.25 —— — 1.25 1.25 1.25 Carbonate 10.0 — 11.0 5.0 2.0 7.0 13.0 9.0 Calcium27.5 39.0 35.0 — — 40.0 — 40.0 carbonate Sulfate 5.0 5.0 3.0 5.0 3.0 — —5.0 TSPP 5.0 — — — — 5.0 2.5 — STPP 5.0 15.0 10.0 — — 7.0 8.0 10.0Bentonite clay — 10.0 — — 5.0 — — — DTPMP — 0.7 0.6 — 0.6 0.7 0.7 0.7CMC — 1.0 1.0 1.0 1.0 — — 1.0 Talc — — 10.0 15.0 10.0 — — — Silicate — —4.0 5.0 3.0 — — — PVNO 0.02 0.03 — 0.01 — 0.02 — — MA/AA 0.4 1.0 — — 0.20.4 0.5 0.4 SRP1 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 Protease — 0.12 — 0.080.08 — — 0.1 Lipase — 0.1 — 0.1 — — — — Amylase — — 0.8 — — — 0.1 —Cellulase — 0.15 — — 0.15 0.1 — — PEO — 0.2 — 0.2 0.3 — — 0.3 Perfume1.0 0.5 0.3 0.2 0.4 — — 0.4 Mg sulfate — — 3.0 3.0 3.0 — — — PARP1 10 —— — — 8 — — (c) (c) PARP2 — 4 — — — — 2 — (c) (c) PARP3 — — 2 — — — — 1(c) (c) PARP4 — — — 4 — — — — (s) PARP5 — — — — 10 — — 4 (c) (c)Brightener 0.15 0.10 0.15 — — — — 0.1 Photoactivated — 15.0 15.0 15.015.0 — — 15.0 bleach (ppm)

EXAMPLE 15

The following detergent additive compositions were prepared according tothe present invention:

A B C LAS — 5.0 5.0 STPP 30.0 — 20.0 Zeolite A — 35.0 20.0 PB1 20.0 15.0— TAED 10.0 8.0 — PARP1 10.0(c) — 5.0(c) PARP3 — 4.0(c) 2.0(c) Protease— 0.3 0.3 Amylase — 0.06 0.06 Minors, water and miscellaneous Up to 100%

EXAMPLE 16

The following compact high density (0.96 Kg/l) dishwashing detergentcompositions were prepared according to the present invention:

A B C D E F G H STPP — — 54.3 51.4 51.4 — — 50.9 Citrate 35.0 17.0 — — —46.1 40.2 — Carbonate — 15.0 12.0 14.0 4.0 — 7.0 31.1 Bicarbonate — — —— — 25.4 — — Silicate 32.0 14.8 14.8 10.0 10.0 1.0 25.0 3.1 Metasilicate— 2.5 — 9.0 9.0 — — — PB1 1.9 9.7 7.8 7.8 7.8 — — — PB4 8.6 — — — — — —— Percarbonate — — — — — 6.7 11.8 4.8 Nonionic 1.5 2.0 1.5 1.7 1.5 2.61.9 5.3 TAED 5.2 2.4 — — — 2.2 — 1.4 HEDP — 1.0 — — — — — — DTPMP — 0.6— — — — — — MnTACN — — — — — — 0.008 — PAAC — — 0.008 0.01 0.007 — — —BzP — — — — 1.4 — — — Paraffin 0.5 0.5 0.5 0.5 0.5 0.6 — — PARP3 2 4 2 1— — — 0.5 (c) (c) (c) (c) (c) PARP1 — — — — 10 3 2 — (c) (s) (c)Protease 0.072 0.072 0.029 0.053 0.046 0.026 0.059 0.06 Amylase 0.0120.012 0.006 0.012 0.013 0.009 0.017 0.03 Lipase — 0.001 — 0.005 — — — —BTA 0.3 0.3 0.3 0.3 0.3 — 0.3 0.3 MA/AA — — — — — — 4.2 — 480N 3.3 6.0 —— — — — 0.9 Perfume 0.2 0.2 0.2 0.2 0.2 0.2 0.1 0.1 Sulphate 7.0 20.05.0 2.2 0.8 12.0 4.6 — pH 10.8 11.0 10.8 11.3 11.3 9.6 10.8 10.9Miscellaneous and water Up to 100%

EXAMPLE 17

The following granular dishwashing detergent compositions of bulkdensity 1.02 Kg/L were prepared according to the present invention:

A B C D E F G H STPP 30.0 30.0 33.0 34.2 29.6 31.1 26.6 17.6 Carbonate29.5 30.0 29.0 24.0 15.0 36.0 2.1 38.0 Silicate 7.4 7.4 7.5 7.2 13.3 3.443.7 12.4 Metasilicate — — 4.5 5.1 — — — — Percarbonate — — — — — 4.0 —— PB1 4.4 4.2 4.5 4.5 — — — — NADCC — — — — 2.0 — 1.6 1.0 Nonionic 1.21.0 0.7 0.8 1.9 0.7 0.6 0.3 TAED 1.0 — — — — 0.8 — — PAAC — 0.004 0.0040.004 — — — — BzP — — — 1.4 — — — — Paraffin 0.25 0.25 0.25 0.25 — — — —PARP3 1.0 0.5 4.0 8.0 — — 1.0 0.5 (c) (c) (s) (c) (c) (c) PARP1 — — — —10 5.0 2.0 8.0 (c) (c) (c) (s) Protease 0.036 0.015 0.03 0.028 — 0.03 —— Amylase 0.003 0.003 0.01 0.006 — 0.01 — — Lipase 0.005 — 0.001 — — — —— BTA 0.15 0.15 0.15 0.15 — — — — Perfume 0.2 0.2 0.2 0.2 0.1 0.2 0.2 —Sulphate 23.4 25.0 22.0 18.5 30.1 19.3 23.1 23.6 pH 10.8 10.8 11.3 11.310.7 11.5 12.7 10.9 Miscellaneous and water Up to 100%

EXAMPLE 18

The following tablet detergent compositions were prepared according tothe present invention by compression of a granular dishwashing detergentcomposition at a pressure of 13 KN/cm² using a standard 12 head rotarypress:

A B C D E F STPP — 48.8 49.2 38.0 — 46.8 Citrate 26.4 — — — 31.1 —Carbonate — 4.0 12.0 14.4 10.0 20.0 Silicate 26.4 14.8 15.0 12.6 17.72.4 PARP1 3.0(c) — — — 5.0(c) — PARP2 — 2.0(c) — — — 4.0(c) PARP3 — —2.0(c) 1(s) — — Protease 0.058 0.072 0.041 0.033 0.052 0.013 Amylase0.01 0.03 0.012 0.007 0.016 0.002 Lipase 0.005 — — — — — PB1 1.6 7.712.2 10.6 15.7 — PB4 6.9 — — — — 14.4 Nonionic 1.5 2.0 1.5 1.65 0.8 6.3PAAC — — 0.02 0.009 — — MnTACN — — — — 0.007 — TAED 4.3 2.5 — — 1.3 1.8HEDP 0.7 — — 0.7 — 0.4 DTPMP 0.65 — — — — — Paraffin 0.4 0.5 0.5 0.55 —— BTA 0.2 0.3 0.3 0.3 — — PA30 3.2 — — — — — MA/AA — — — — 4.5 0.55Perfume — — 0.05 0.05 0.2 0.2 Sulphate 24.0 13.0 2.3 — 10.7 3.4 Weightof 25 g 25 g 20 g 30 g 18 g 20 g tablet pH 10.6 10.6 10.7 10.7 10.9 11.2Miscellaneous Up to 100% and water

EXAMPLE 19

The following liquid dishwashing detergent compositions of density 1.40Kg/L were prepared according to the present invention:

A B C D STPP 17.5 17.5 17.2 16.0 Carbonate 2.0 — 2.4 — Silicate 5.3 6.114.6 15.7 NaOCl 1.15 1.15 1.15 1.25 Polygen/carbopol 1.1 1.0 1.1 1.25Nonionic — — 0.1 — NaBz 0.75 0.75 — — PARP3 4.0(c) 2.0(c) 1.0(c) 0.5(c)NaOH — 1.9 — 3.5 KOH 2.8 3.5 3.0 — pH 11.0 11.7 10.9 11.0 Sulphate,miscellaneous and water up to 100%

EXAMPLE 20

The following liquid rinse aid compositions were prepared according tothe present invention:

A B C Nonionic 12.0 — 14.5 Nonionic blend — 64.0 — Citric 3.2 — 6.5 HEDP0.5 — — PEG — 5.0 — SCS 4.8 — 7.0 Ethanol 6.0 8.0 — PARP5 6.0(c) —3.0(c) PARP3 — 2.0(c) 1.0(c) pH of the liquid 2.0 7.5 / Miscellaneousand water Up to 100%

EXAMPLE 21

The following liquid dishwashing compositions were prepared according tothe present invention:

A B C D E C17ES 28.5 27.4 19.2 34.1 34.1 Amine oxide 2.6 5.0 2.0 3.0 3.0C12 glucose amide — — 6.0 — — Betaine 0.9 — — 2.0 2.0 Xylene sulfonate2.0 4.0 — 2.0 — Neodol C11E9 — — 5.0 — — Polyhydroxy fatty — — — 6.5 6.5acid amide Sodium diethylene — — 0.03 — — penta acetate (40%) TAED — — —0.06 0.06 Sucrose — — — 1.5 1.5 Ethanol 4.0 5.5 5.5 9.1 9.1 Alkyldiphenyl — — — — 2.3 oxide disulfonate Ca formate — — — 0.5 1.1 Ammoniumcitrate 0.06 0.1 — — — Na chloride — 1.0 — — — Mg chloride 3.3 — 0.7 — —Ca chloride — — 0.4 — — Na sulfate — — 0.06 — — Mg sulfate 0.08 — — — —Mg hydroxide — — — 2.2 2.2 Na hydroxide — — — 1.1 1.1 Hydrogen peroxide200 ppm 0.16 0.006 — — PARP3 4.0(c) — 2.0(c) — 0.25(c) PARP1 — 6.0(c) —4.0(s) 3(c) Protease 0.017 0.005 .0035 0.003 0.002 Perfume 0.18 0.090.09 0.2 0.2 Water and minors Up to 100%

EXAMPLE 22

The following liquid hard surface cleaning compositions were preparedaccording to the present invention:

A B C D E PARP1 8.0(c) — 6.0(s) — 4.0(c) PARP3 — 2.0(c) — 1.0(c) 0.5(c)Amylase 0.01 0.002 0.005 — — Protease 0.05 0.01 0.02 — — Hydrogenperoxide — — — 6.0 6.8 Acetyl triethyl citrate — — — 2.5 — DTPA — — —0.2 — Butyl hydroxy toluene — — — 0.05 — EDTA* 0.05 0.05 0.05 — —Citric/Citrate 2.9 2.9 2.9 1.0 — LAS 0.5 0.5 0.5 — — C12 AS 0.5 0.5 0.5— — C10AS — — — — 1.7 C12(E)S 0.5 0.5 0.5 — — C12,13 E6.5 nonionic 7.07.0 7.0 — — Neodol 23-6.5 — — — 12.0 — Dobanol 23-3 — — — — 1.5 Dobanol91-10 — — — — 1.6 C25AE1.8S — — — 6.0 Na paraffin sulphonate — — — 6.0Perfume 1.0 1.0 1.0 0.5 0.2 Propanediol — — — 1.5 Ethoxylatedtetraethylene — — — 1.0 — pentaimine 2, Butyl octanol — — — — 0.5 Hexycarbitol** 1.0 1.0 1.0 — — SCS 1.3 1.3 1.3 — — pH adjusted to 7-12 7-127-12 4 — Miscellaneous and water Up to 100% *Na4 ethylenediaminediacetic acid **Diethylene glycol monohexyl ether

EXAMPLE 23

The following spray composition for cleaning of hard surfaces andremoving household mildew was prepared according to the presentinvention:

PARP3 4.0(c) Amylase 0.01 Protease 0.01 Na octyl sulfate 2.0 Na dodecylsulfate 4.0 Na hydroxide 0.8 Silicate 0.04 Butyl carbitol* 4.0 Perfume0.35 Water/minors up to 100% *Diethylene glycol monobutyl ether

EXAMPLE 24

The following lavatory cleansing block compositions were preparedaccording to the present invention.

A B C C16-18 fatty alcohol/50EO 70.0 — — LAS — — 80.0 Nonionic — 1.0 —Oleoamide surfactant — 25.0 — Partially esterified copolymer ofvinylmethyl 5.0 — — ether and maleic anhydride, viscosity 0.1-0.5Polyethylene glycol MW 8000 — 38.0 — Water-soluble K-polyacrylate MW4000-8000 — 12.0 — Water-soluble Na-copolymer of acrylamide — 19.0 —(70%) and acryclic acid (30%) low MW Na triphosphate 10.0 — — Carbonate— — — PARP5 8.0(c) — 6.0(c) PARP3 — 2.0(c) 0.5(c) Dye 2.5 1.0 1.0Perfume 3.0 — 7.0 KOH/HCL solution pH 6-11

EXAMPLE 25

The following toilet bowl cleaning composition was prepared according tothe present invention.

A B C14-15 linear alcohol 7EO 2.0 10.0 Citric acid 10.0 5.0 PARP2 2.0(c)— PARP3 — 4.0(c) DTPMP — 1.0 Dye 2.0 1.0 Perfume 3.0 3.0 NaOH pH 6-11Water and minors Up to 100%

EXAMPLE 26

The following fabric softening compositions are in accordance with thepresent invention:

Component A B C D E F DTDMAC — — — — 4.5 15.0 DEQA 2.6 2.9 18.0 19.0 — —Fatty acid 0.3 — 1.0 — — — HCl 0.02 0.02 0.02 0.02 0.02 0.02 PEG — — 0.60.6 — 0.6 Perfume 1.0 1.0 1.0 1.0 1.0 1.0 Silicone antifoam 0.01 0.010.01 0.01 0.01 0.01 PARP 3 4.5(c) 1.0(c) 3.0(s) 3.0(c) 1.0(s) 6.0(c)Electrolyte (ppm) — — 600 1200 — 1200 Dye (ppm) 10 10 50 50 10 50 Waterand minors to balance to 100%

EXAMPLE 27

The following dryer added fabric conditioner compositions were preparedaccording to the present invention:

A B C D DEQA(2) — — — 50.0 DTMAMS — — 26.0 — SDASA 70.0 70.0 42.0 35.0Neodol 45-13 13.0 13.0 — — Ethanol 1.0 1.0 — — PARP 3(c) 1.5 — 1.5 3.0PARP 3(s) — 1.5 — — Perfume 0.75 0.75 1.0 1.5 Glycoperse S-20 — — — 10.0Glycerol — — 26.0 — monostearate Digeranyl Succinate 0.38 0.38 — — Clay— — 3.0 — Dye 0.01 0.01 — — Minors to balance to 100%

EXAMPLE 28

The following are non-limiting examples of pre-soak fabric conditioningand/or fabric enhancement compositions according to the presentinvention which can be suitably used in the laundry rinse cycle.

Ingredients A B C D E F Polymer 3.5 3.5 3.5 3.5 3.5 3.5 Dye fixative 2.32.3 2.4 2.4 2.5 2.5 Polyamine 15.0 15.0 17.5 17.5 20.0 20.0 Bayhibit AM1.0 1.0 1.0 1.0 1.0 1.0 C₁₂—C₁₄ dimethyl — 5.0 5.0 — — — hydroxyethylquaternary ammonium chloride Fabric softener active — — 2.5 2.5 — —Genamin C100 0.33 — 0.33 0.33 0.33 — Genapol V4463 0.2 — 0.2 0.2 0.2 —PARP3(c) 15 30 1.5 7.5 0.75 1.0 Water & minors bal- bal- bal- bal- bal-bal- ance ance ance ance ance ance

EXAMPLE 29

The following are non-limiting examples of odor-absorbing compositionssuitable for spray-on applications:

Examples A B C D E HPBCD 1.0 — 1.0 — 1.2 RAMEB — 1.0 — 0.8 — Tetronic901 — — 0.1 — — Silwet — — — 0.1 — L-7604 Silwet 0.1 — — — 0.1 L-7600Bardac 2050 — — —  0.03 — Bardac 2250 — 0.2 — — 0.1 Diethylene — 1.0 — —0.2 glycol Triethylene — — 0.1 — — glycol Ethanol — — — — 2.5 Perfume 10.1 — — — — Perfume 2 —  0.05 — 0.1 — Perfume 3 — — 0.1 — 0.1 Kathon 3ppm 3 ppm 3 ppm 3 ppm — HCI to pH 4.5 to pH 4.5 to pH 3.5 to pH 3.5 topH 3.5 PARP3(c) 10.0  10.0  5.0 1.0 0.8 Distilled Bal. Bal. Bal. Bal.Bal. water

The perfume 1, 2, and 3 have the following compositions:

Perfume 1 2 3 Perfume Ingredients Wt. % Wt. % Wt. % Anisic aldehyde — —2 Benzophenone 3  5 — Benzyl acetate 10  15 5 Benzyl salicylate 5 20 5Cedrol 2 — — Citronellol 10  — 5 Coumarin — — 5 Cymal — — 3Dihydromyrcenol 10  — 5 Flor acetate 5 — 5 Galaxolide 10  — — Lilial 10 15 20  Linalyl acetate 4 — 5 Linalool 6 15 5 Methyl dihydro jasmonate 310 5 Phenyl ethyl acetate 2  5 1 Phenyl ethyl alcohol 15  15 20 alpha-Terpineol 5 — 8 Vanillin — — 1 Total 100  100  100 

What is claimed is:
 1. A process for making particles of amine reaction product of a compound containing a primary and/or secondary amine functional group selected from the group consisting of aminoaryl derivatives, polyamines, amino acids and derivatives thereof, substituted amines, polyaminoacids, glucamines, dendrimers, polyvinylamines with a molecular weight of from 600 to 50,000, amino substituted polyvinylalcohol with a molecular weight ranging from 400 to 300,000, polyoxyethylene bis(amine), polyoxyethylene bis(6-aminohexyl), N-N′-bis-(3-aminopropyl)-1,3-propanediamine linear or branched, 1,4-bis-(3-aminopropyl)piperazine, and mixtures thereof; and an active ketone or aldehyde containing component a flavour ketone or aldehyde ingredient, a pharmaceutical ketone or aldehyde active, a biocontrol aldehyde or ketone agent, a perfume, a refreshing cooling ketone or aldehyde agent, an insect and/or moth repellent, an antimicrobial, and mixtures thereof; and which comprises the steps of: a)-providing an amine reaction product, and b)-mixing therewith a carrier selected from the group consisting of organic polymeric compounds, waxes, paraffins, oils, glycerides, monoglycerides, diglycerides, riglycerides, anionic surfactants, nonionic surfactants, cationic surfactants, zwitterionic surfactants, and mixtures thereof, having a melting point between 30° C. and 135° C., wherein the amount of amine reaction product ranges from 1 to 75% by weight of the processed amine reaction product.
 2. A process according to claim 1, wherein said particle is treated to form a coated particle.
 3. A process according to claim 1, wherein the amine reaction product has a viscosity of higher than 1000 cps.
 4. A process according to claim 1, wherein the carrier has a melting point between 45° C. and 85° C.
 5. A process according to claim 1, wherein the amount of carrier material ranges from 3 to 95%, by weight of the produced particles of the processed amine reaction product.
 6. A process according to claim 5, wherein the coating is made of water-soluble agglomerating agent.
 7. A process according to claim 6, wherein the water-soluble agglomerating agent is selected from water soluble organic polymeric compounds, water soluble monomeric polycarboxylates, or their acid forms, homo or copolymeric polycarboxylic acids or their salts in which the polycarboxylic acid comprises at least two carboxylic radicals separated from each other by not more that two carbon atoms, carbonates, bicarbonates, borates, phosphates, sulfate salts, inorganic perhydrate salts, silicates, starch, cyclodextrin, and mixtures thereof.
 8. A processed amine reaction product produced by the process of claim
 1. 9. A finished composition comprising one or more laundry or cleaning ingredient and a processed amine reaction product according to claim
 6. 10. A composition according to claim 9, wherein said composition is selected from a laundry composition, hard surface cleaning composition, personal cleaning composition.
 11. A composition according to claim 10, wherein the composition is a detergent composition comprising a clay.
 12. A method for delivering residual fragrance to a surface which comprises the steps of contacting said surface with a processed product according to claim 8 or claim 4, and thereafter contacting the treated surface with a material so that the perfume is released.
 13. A packaged composition comprising the detergent composition of claim
 11. 14. A process according to claim 1 wherein the amount of amine reaction product ranges from 5 to 30%, by weight of the processed amine reaction product.
 15. A process according to claim 5 wherein the amount of carrier material ranges from 15 to 80% by weight of the produced particles of the processed amine reaction product.
 16. A process according to claim 15 wherein the amount of carrier material ranges from 25 to 75% by weight of the produced particles of the processed amine reaction product.
 17. A process according to claim 5 wherein the amount of amine reaction product ranges from 5 to 30% by weight of the coated particle. 